PL84012B1 - - Google Patents

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PL84012B1
PL84012B1 PL1973162554A PL16255473A PL84012B1 PL 84012 B1 PL84012 B1 PL 84012B1 PL 1973162554 A PL1973162554 A PL 1973162554A PL 16255473 A PL16255473 A PL 16255473A PL 84012 B1 PL84012 B1 PL 84012B1
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PL
Poland
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cyano
alkyl
radical
methyl
general formula
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PL1973162554A
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Polish (pl)
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Imperial Chemical Industries Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/78Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84Nitriles
    • C07D213/85Nitriles in position 3
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00Monoazo dyes prepared by diazotising and coupling
    • C09B29/34Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3617Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
    • C09B29/3621Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
    • C09B29/3626Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O)
    • C09B29/363Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O) from diazotized amino carbocyclic rings

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Description

Przedmiotem wynalazku jest sposób wytwarza¬ nia barwników monoazowych nierozpuszczalnych w wodzie, wartosciowych do barwienia syntetycz¬ nych materialów wlókienniczych, szczególnie do barwienia wlókien z poliestrów aromatycznych. 5 W polskim opisie patentowym nr 77 107 podano sposób wytwarzania barwników monoazowych nie¬ rozpuszczalnych w wodzie, wolnych od grup sul¬ fonowych i karboksylowych, stanowiacych jedna z mozliwych postaci tautometrycznych zwiazków 10 o ogólnym wzorze 1, w którym A oznacza rodnik arylowy ewentualnie podstawiony, n oznacza war¬ tosc liczbowa zero lub 1, Z oznacza rodnik alki¬ lowy lub arylowy ewentualnie podstawiony, jeden z symboli X1 i X2 oznacza atom wodoru lub rod- 15 nik alkilowy albo arylowy ewentualnie podstawio¬ ny, lub grupe -CN, -COOR, -COR albo -CONRiR2, a drugi z symboli X1 i X2 oznacza grupe -CN, COOR, -COR lub CONRJR2, w którym R oznacza rodnik alkilowy lub arylowy ewentualnie podsta- 20 wiony, a R1 i R2 kazdy niezaleznie oznacza atom wodoru lub rodnik alkilowy albo arylowy ewen¬ tualnie podstawiony, lub R1 i R2 razem tworza z atomem azotu piecio lub szescioczlonowy pierscien heterocykliczny zawierajacy azot. Barwniki te, 25 chociaz barwia poliestrowe materialy wlókiennicze, dajac zabarwienia o doskonalej trwalosci na dzia¬ lanie swiatla i duzej odpornosci na sucha obróbke cieplna, to jednak w przypadku istosowania barw¬ ników O wzorze 1, w którym A oznacza rodnik 30 fenylowy zawierajacy elektroujemny podstawnik, taki jak grupa nitrowa, X2 oznacza grupe cyjano- wa a Z oznacza nizszy rodnik alkilowy, barwniki takie sa zbytnio wrazliwe na zmiane pH kapieli barwiacej.Stwierdzono, ze te niedogodnosc mozna zmniej¬ szyc lub nawet calkowicie usunac, jezeli w proce¬ sie barwienia stosuje sie barwniki o wzorze 1, w którym Z oznacza rodnik alkilowy o co najmniej 5 atomach wegla.Wedlug wynalazku wytwarza sie barwniki mo- noazowe nierozpuszczalne w wodzie, stanowiace jedna z mozliwych postaci tautometrycznych zwiazków o ogólnym wzorze 2, w którym A2 o- znacza rodnik fenylowy podstawiony grupa nitro¬ wa, cyjnanowa, trójfluorometylowa lub grupa o wzorze -S02R3, -CONR4R5 lub -COR3 i który ewen¬ tualnie jest podstawiony jedna lub dwiema gru¬ pami nitrowymi, cyjanowymi, nizszymi rodnikami alkoksylowymi, nizszymi rodnikami alkoksylowymi zawierajacymi grupe -OH nizszymi rodnikami al¬ koksylowymi zawierajacymi grupe acyloksylowa, nizszymi rodnikami alkilowymi lub fenoksylowy- mi, przy czym R3 oznacza rodnik alkilowy, cyklo- alkilowy, arylowy lub aralkilowy, R4 oznacza atom wodoru lub rodnik alkilowy, cykloalkilowy, ary¬ lowy albo aralkilowy, R5 oznacza atom wodoru lub rodnik alkilowy, a Z2 oznacza rodnik alkilowy o co najmniej 5 atomach wegla.Korzystnymi rodnikami alkilowymi dla R3, R4 i 84 01284 012 R5 sa rodniki alkilowe o 1—10 atomach wegla, ta¬ kie jak rodnik metylowy, etylowy, n-propylowy, n-butylowy, amylowy, heksylowy, oiktylowy, dwu- metyloheksylowy i dodecylowy.Korzystnym rodnikiem cykloalkilowym dla R3 i R4 jest rodnik cykloheksylowy.Korzystnymi rodnikami arylowymi dla R3 i R4 sa rodniki jednopierscieniowe, takie jak rodnik fe- nylowy, tolilowy i ksylilowy, a jako rodnik aral- kilowy — rodnik fenylowy podstawiony nizszym rodnikiem alkilowym, taki jak rodnik benzylowy i B-fenyloetylowy.Jako przyklad nizszych rodników alkoksylowych podstawionych grupa -OH wymienia sie grupe B-hydroksyetoksylowa i yriydroksypropoksylowa, a jako nizszy rodnik alkoksylowy podstawiony gru¬ pa acyloksylowa wymienia sie np. rodnik B-aceto- ksyetoksylowy.Korzystnymi rodnikami alkilowymi o co naj¬ mniej 5 atomach wegla, oznaczonymi symbolem Z2, sa rodniki alkilowe o 5—12 atomach wegla, ta¬ kie jaik rodnik amylowy, heksylowy, oktylowy, de- cylowy, dodecylowy i dwumetyloheksylowy.Stosowane w opisie okreslenie rodników „nizszy alkilowy" i „nizszy alkoksylowy" oznaczaja rod¬ niki o 1—4 atomach wegla, takie jak rodnik me¬ tylowy, etylowy, metoksylowy, etoksylowy, buto- ksylowy.Barwniki monoazowe wytwarzane sposobem we¬ dlug wynalazku moga wystepowac w licznych po¬ staciach tautometrycznych, lecz w celu uproszcze¬ nia zostaly one okreslone jedna z ich postaci. Na¬ lezy jednak rozumiec, ze wynalazek obejmuje swym zakresem barwniki we wszystkich mozliwych ich formach tautometrycznych.Sposobem wedlug wynalazku wytwarzania barw¬ ników monoazowych nierozpuszczalnych w wodzie, stanowiacych jedna z mozliwych postaci tautome¬ trycznych zwiazków o ogólnym wzorze 2, w któ¬ rym A2 i Z2 maja wyzej podane znaczenie, polega na tym, ze amine o ogólnym wzorze A2-NH2, w którym A2 ma wyzej podane znaczenie, poddaje sie dwuazowaniu i wytworzony zwiazek dwuazowy sprzega sie ze skladnikiem biernym o ogólnym wzorze 3, w którym Z2 ma wyzej podane znaczenie.Jako przyklad aminy o wzorze A2-NH wymienia sie 2-, 3- lub 4-nitroaniline, 2,4-dwunitroaniline, 2- lub 4-tcyjano-, metylo-, lub metoksy-)4- lub 2- -nitroaniline, 2,6-dwu(chloro- lub bromo)-4-nitro- aniline, 4-aminobenzotrójfluorek, 4-cyjanoaniline, 2,4-dwucyjanoaniiline, 4-metylosulfonyloaniline, 4- -acetyloaniline, 2-, 3- lub 4-amino-benzenokarbo- namid i 2-, 3- lub 4-aminobenzenokarbo-N-(me- tylo-, etylo-, amylo-, heksylo- lub oktylo-)-amid.Skladniki bierne o wzorze 3 moga byc wytwo¬ rzone przez kondensacje acetylooctanu etylu, cy- janooctanu etylu i odpowiedniej aminy o ogólnym wzorze Z2-NH2, w którym Z2 ma wyzej podane znaczenie.Jako przyklad takich skladników biernych wy¬ mienia sie l-(amylo-, heksylo-, dwumetyloheksy- lo-, oktylo- lub decylo-)-cyjano-4-metylo-6-hy- droksyipirydon-2.Barwniki monoazowe nierozpuszczalne w wodzie, wytwarzane sposobem wedlug wynalazku, maja zastosowanie do barwienia syntetycznych materia¬ lów wlókienniczych, szczególnie do barwienia wló- kien z poliestrów aromatycznych metodami poda¬ nymi w brytyjskim opisie patentowym nr 1 249 641.Barwniki te daja doskonale wybarwienia powyz¬ szych materialów wlókienniczych w odcieniach od zólto-zielonych do pomaranczowo-czerwonych i wykazuja na wlóknie bardzo mala odpornosc na dzialanie swiatla oraz na ogrzewanie w stanie su¬ chym i wilgotnym. W szczególnosci, barwniki wy¬ tworzone sposobem wedlug wynalazku wykazuja wyzszosc w stosunku do znanych barwników o ogólnym wzorze 1, w którym Z oznacza nizszy rodnik alkilowy, tym, ze sa o wiele mniej wraz¬ liwe na zmiany wartosci pH kapieli barwiacej.W nizej podanych przykladach czesci oznaczaja czesci wagowe.Przyklad I. Do mieszaniny 25 czesci wody i 25 czesci lodu wlano roztwór 2,8 czesci 2-nitro- aniliny w 20 czesciach 43% roztworu wodnego kwasu siarkowego i stale mieszajac oraz utrzymu¬ jac temperature 0—5°C przez chlodzenie z zew- natrz, dodano 10 czesci 14% roztworu wodnego azotynu sodu, po czym mieszano jeszcze 15 minut w temperaturze 0—5°C.Otrzymana mieszanine wlano powoli do roztworu ,24 czesci l-(2-etyloheksylo)-3-cyjano-4-metylo-6- hydroksypirydonu-2 i 6 czesci octanu sodu w 100 czesciach 1% roztworu wodnego wodorotlenku so¬ du, stale mieszajac i utrzymujac temperature 0—5°C przez chlodzenie z zewnatrz, nastepnie mieszano jeszcze w ciagu 30 minut, po czym wy- tracony barwnik odsaczono, przemyto woda i wy¬ suszono.Otrzymany barwnik, uzyty w postaci zawiesiny wodnej, wybarwial materialy wlókiennicze z po¬ liestru aromatycznego na odcienie zólto-zielone, o doskonalej odpornosci na dzialanie swiatla oraz na ogrzewanie w stanie suchym i wilgotnym, przy czym wykazywal o wiele mniejsza wrazliwosc na zmiany wartosci pH kapieli barwiacej niz znane barwniki o ogólnym wzorze 1, opisane wyzej. l-(2' -etyloheksylo)-3-cyjnaino-4-metylo-6-hydrok- sypirydon-2, uzyty jako czynnik bierny, otrzyma¬ no przez kondensacje acetylooctanu etylu, cyjnano- octanu etylu i 2-etyloheksyloaminy. 50 Zamiast 2,8 czesci 2-nitroaniliny uzyto w po¬ wyzszym przykladzie 3,36 czesci 4-metoksy-2-nitro- aniliny lub 2-metoksy-4-nitroaniliny i otrzymano podobne barwniki.W ponizszej tablicy podano dalsze przyklady 55 barwników, które otrzymano przez zdwuazowanie aminy wymienionej w 2 kolumnie tablicy i sprze¬ zenie otrzymanego zwiazku dwuazowego ze sklad¬ nikiem biernym wymienionym w 3 kolumnie, pro¬ wadzac proces w taki sam sposób jak opisano w przykladzie I. W 4 kolumnie podano odcienie wy¬ barwienia barwników uzytych do materialów wló¬ kienniczych z poliestrów aromatycznych. 40 45 6084 012 Tablica 1 Przyklad " * " II III IV V VI VII VIII IX X XI XII XIII XIV XV XVI XVII XVIII XIX XX XXI XXII 1 XXIII XXIV xxv XXVI XXVII XXVIII XXIX xxx XXXI XXXII XXXIII XXXIV xxxv XXXVI XXXVII XXXVIII Amina 2~ 2,4-dwunitroanilina -2(amino-5-nitrofenoksyetanol 2-nitroanilina 4-metoksy-2-nitroanilina 4-aminobenzenoamid 4-aminobenzeno-N-etyloamid 4-aminobenzeno-N,N-dwuety- loamid 4-metylo-2-nitroanilina 2-metylo-4-nitroanilina 2-metylo-5-nitroanilina 2-nitroanilina — „ — — " — — » — — „ — 3-nitroanilina 4-'nitroanilina 2-metoksy-5-nitroanilina 2-cyjano-4-nitroanilina 4-metylosulfonyloanilina 2-trójfluorometyloanilina 4-acetyloanilina eter 2-amino-5-nitrodwufeny- lowy 2-fenylosulfonyloanilina 2-metoksy-4-nitroanilina 2-(B-acetoksyetoksy)-4-nitroani- lina 4-benzylosulfonyloanilina 4-cykloheksylosulfonyloanilina 4-benzoiloanilina 4-(p-metylobenzoilo) anilina 4-cykloheksylokarbonyloanilina 4-(B-fenyloetylokarbonylo)ani- lina 2,4-dwunitro-6-metylanilina 2,4-dwunitro-6-metylanilina 2,3-dwumetoksy-5-nitroanilina 2-metylo-5-metoksy-4-nitroani- lina 2,4-dwumetylo-6-nitroanilina Skladnik bierny 3 l-(2-etyloheksylo-3-cyjano-4-metylo- -6-hydroksypirydon-2 ~~" 55 ' 55 l-(n-oktylo)-3-cyjano-4-metylo-6- hydroksypirydon-2 55 55 — 55 — — „ ~ — 5, — — „ — — 5, — — „ — 55 JJ 55 55 55 JJ l-n-pentylo-3-cyjano-4-metylo-6-hy- droksypirydon-2 l-n-heksylo-3-cyjano-4-metylo-6- -hydroksypirydon-2- l-n-heptylo-3-cyjano-4-metylo-6- -hydroksypirydon-2 l-n-decylo-3-cyjano-4-metylo-6- -hydroksypirydynon-2 l-n-dodecylol3-cyjnano-4-metylo-6- -hydroksypirydon-2 l-n-oktylo-3-cyjano-4-metylo-6-hy- droksypirydon-2 — 55 — — „ — — 55 — —55 ~ — ,, — — „ — l-n-oktylo-3-cyjano-4-metylo-6-hy- droksypirydon-2 — „ — — „ — — „ — — „ — — 55 — — „ ~ — 55 — — 5, ~ l-n-oktylo-3-cyjano-4-metylo-6-hy- droksypirydon-2 — 55 — — 55 — — 5, — — ,5 ~ — 55 — — 55 — — „ — — „ — — 55 — — 5, — 55 55 l-n-oktylo-3-cyjano-4-metylo-6-hy- droksypirydon-2 55 JJ 55 55 55 55 55 JJ Odcien 4 zólto-zielony zólto-czerwony zólto-zielony pomaranczowy zólto-zielony — » — — » — zólto-czerwony " zólto-zielony — „ — — „ — — » — — " — 55 — „ — — „ — zólto-czerwony zólto-zielony zólto-zielony — „ — — „ — — „ — — „ — zólto-zielony zólto-czerwony — „ — — „ — — „ — — „ — zólto-zielony — „ — zólty zólto-czerwony oranzowy PLThe present invention relates to a process for the production of water-insoluble monoazo dyes of value for dyeing synthetic textiles, especially for dyeing aromatic polyester fibers. 5 Polish patent specification No. 77 107 describes a method of producing monoazo dyes insoluble in water, free from sulfonic and carboxyl groups, which are one of the possible tautometric forms of compounds of general formula I, in which A is an optionally substituted aryl radical, n represents a numerical value of zero or 1, Z is an optionally substituted alkyl or aryl radical, one of the symbols X1 and X2 is a hydrogen atom or an optionally substituted alkyl or aryl radical, or a -CN, -COOR group , -COR or -CONRiR2, and the other X1 and X2 represents the group -CN, COOR, -COR or CONRJR2, where R is an optionally substituted alkyl or aryl radical, and R1 and R2 each independently represent a hydrogen atom or an optionally substituted alkyl or aryl radical, or R1 and R2 together form a five or six membered nitrogen containing heterocyclic ring with the nitrogen atom. These dyes, although they dye polyester textiles, give dyes with excellent light fastness and high resistance to dry heat treatment, however, when using dyes of formula I, in which A is a phenyl radical having an electronegative substituent such as a nitro group, X2 represents a cyano group and Z represents a lower alkyl radical, such dyes are too sensitive to a change in the pH of the dye bath. It has been found that this inconvenience can be reduced or even completely eliminated if by dyeing dyes of formula I are used in which Z is an alkyl radical of at least 5 carbon atoms. According to the invention, water-insoluble mono-dyes are produced, which are one of the possible tautometric forms of compounds of formula II, in which A2 is a phenyl radical substituted with a nitro, cyano, trifluoromethyl group or a group of the formula -SO2R3, -CONR4R5 or -COR3, and which optionally eat is substituted with one or two nitro, cyano, lower alkoxy radicals, lower alkoxy radicals containing the —OH group, lower alkoxy radicals containing an acyloxy group, lower alkyl or phenoxy radicals, where R3 is an alkyl, cycloalkyl radical , aryl or aralkyl, R4 is a hydrogen atom or an alkyl, cycloalkyl, aryl or aralkyl radical, R5 is a hydrogen atom or an alkyl radical, and Z2 is an alkyl radical of at least 5 carbon atoms. Preferred alkyl radicals for R3, R4 and 84 are No. 01284 012 R5 are alkyl radicals with 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, amyl, hexyl, ethyl, dimethylhexyl and dodecyl radicals. The preferred cycloalkyl radical for R3 and R4 is cyclohexyl radical. Preferred aryl radicals for R3 and R4 are single ring radicals, such as phenyl, tolyl and xylyl radicals, and as the aralkyl radical A phenyl radical substituted with a lower alkyl radical, such as a benzyl radical and a B-phenylethyl radical. As an example of lower alkoxy radicals substituted with an -OH group, B-hydroxyethoxy and yrihydroxypropoxy groups are mentioned, and the lower alkoxy radicals substituted with an acyloxy group are e.g. B-acetoxyethoxy radical. Preferred alkyl radicals with at least 5 carbon atoms, denoted by the symbol Z2, are alkyl radicals with 5 to 12 carbon atoms, such as amyl, hexyl, octyl, decyl, dodecyl and dimethylhexyl. The term "lower alkyl" and "lower alkoxy" radicals as used herein refers to radicals having 1 to 4 carbon atoms, such as methyl, ethyl, methoxy, ethoxy, butoxyl. the debts of the invention may appear in numerous tautometric forms, but for the sake of simplicity, one form has been defined. It should be understood, however, that the scope of the invention includes dyes in all possible tautometric forms. The method of the invention is the preparation of water-insoluble monoazo dyes, which are one of the possible tautometric forms of compounds of the general formula II, in which A2 and Z2 have the above meaning, consisting in that the amine of the general formula A2-NH2, in which A2 has the above meaning, is diazotized and the diazotium compound produced is coupled with the passive component of the general formula 3, in which Z2 has the above the given meaning. Examples of amines of formula A2-NH include 2-, 3- or 4-nitroaniline, 2,4-dinitroaniline, 2- or 4-thcyano-, methyl- or methoxy-) 4- or 2- - nitroaniline, 2,6-di (chloro- or bromo) -4-nitroaniline, 4-aminobenzotrifluoride, 4-cyanoaniline, 2,4-dicyaniline, 4-methylsulfonylaniline, 4-acetylaniline, 2-, 3- or 4 -amino-benzenecarbamide and 2-, 3- or 4-aminobenzenecarbo-N- (methyl-, ethyl-, amy lo-, hexyl or octyl) amide. The passive components of formula III may be prepared by the condensation of ethyl acetoacetate, ethyl cyanoacetate and the corresponding amine of the general formula Z2-NH2 in which Z2 is as defined above. An example of such passive components is 1- (amyl-, hexyl-, dimethylhexyl-, octyl- or decyl-) - cyano-4-methyl-6-hydroxyipyridone-2. Water insoluble monoazo dyes produced according to the invention, they can be used for dyeing synthetic textiles, in particular for dyeing aromatic polyester fibers with the methods described in British Patent No. 1,249,641. These dyes give excellent dyeing of the above textiles in shades of yellow. They are green to orange-red and show very little resistance to the action of light and to heating in a dry and moist state. In particular, the dyes prepared by the process of the invention are superior to the known dyes of the general formula I, wherein Z is a lower alkyl radical, in that they are much less sensitive to changes in the pH value of the dye bath. In the examples, parts denote parts by weight. Example I. A solution of 2.8 parts of 2-nitroaniline in 20 parts of a 43% aqueous solution of sulfuric acid is poured into a mixture of 25 parts of water and 25 parts of ice, and the temperature is kept at 0-5 ° C. C by cooling from the outside, 10 parts of a 14% aqueous solution of sodium nitrite were added, and then stirred for a further 15 minutes at a temperature of 0-5 ° C. The resulting mixture was slowly poured into the solution, 24 parts of 1- (2-ethylhexyl) -3 -cyano-4-methyl-6-hydroxypyridone-2 and 6 parts of sodium acetate in 100 parts of a 1% aqueous solution of sodium hydroxide, stirring constantly and keeping the temperature at 0-5 ° C by cooling with the outside, then stirring for a further 30 minutes, followed by the lost color The dye was drained, washed with water and dried. The resulting dye, used in the form of a water suspension, dyed textiles from aromatic polyester to yellow-green shades, with excellent resistance to light and heating in a dry and moist state, while showed a much lower sensitivity to changes in the pH value of the dye bath than the known dyes of the general formula 1 described above. 1- (2'-ethylhexyl) -3-cyanine-4-methyl-6-hydroxypyridone-2, used as an inert agent, was obtained by condensation of ethyl acetoacetate, ethyl cyanacetate and 2-ethylhexylamine. 50 Instead of 2.8 parts of 2-nitroaniline, 3.36 parts of 4-methoxy-2-nitroaniline or 2-methoxy-4-nitroaniline were used in the above example to obtain similar dyes. Further examples of 55 dyes are given in the table below. which were obtained by the diazotization of the amine mentioned in column 2 of the table and by coupling the diazo compound obtained with the inactive compound mentioned in column 3, carrying out the process in the same way as described in example I. Column 4 gives the shades of dye used for aromatic polyester textiles. 40 45 6084 012 Table 1 Example "*" II III IV V VI VII VIII IX X XI XII XIII XIV XV XVI XVII XVIII XIX XXI XXII 1 XXIII XXIV xxv XXVI XXVII XXVIII XXIX xxx XXXI XXXII XXXIII XXXIV xxxv XXXVI XXXVII XXXVIII Amina 2 ~ 2,4-dinitroaniline -2 (amino-5-nitrophenoxyethanol 2-nitroaniline 4-methoxy-2-nitroaniline 4-aminobenzenamide 4-aminobenzene-N-ethylamide 4-aminobenzene-N, N-diethylamide 4-methyl-2 -nitroaniline 2-methyl-4-nitroaniline 2-methyl-5-nitroaniline 2-nitroaniline - "- -" - - »- -" - 3-nitroaniline 4-'nitroaniline 2-methoxy-5-nitroaniline 2-cyano-4 -nitroaniline 4-methylsulfonylaniline 2-trifluoromethylaniline 4-acetylaniline 2-amino-5-nitro diphenyl ether 2-phenylsulfonylaniline 2-methoxy-4-nitroaniline 2- (B-acetoxyethoxy) -4-nitroaniline 4-nitroaniline 4-benzylsulfonyl-benzylsulfonyl 4-benzoylaniline 4- (p-methylbenzoyl) aniline 4-cyclohexylcarbonyl aniline 4- (B-phenylethylcarbonyl) aniline 2,4-dinitro-6-methylaniline 2,4-dinitro-6-methylaniline 2,3-dimethoxy-5-nitroaniline 2-methyl-5-methoxy-4-nitroaniline 2,4-dimethyl-6-nitroaniline Reactive component 3 1- (2-ethylhexyl-3-cyano-4-methyl- - 6-hydroxypyridone-2 ~~ "55 '55 l- (n-octyl) -3-cyano-4-methyl-6-hydroxypyridone-2 55 55 - 55 - -" ~ - 5, - - "- - 5, - - "- 55 JJ 55 55 55 JJ ln-pentyl-3-cyano-4-methyl-6-hydroxypyridone-2 ln-hexyl-3-cyano-4-methyl-6- hydroxypyridone-2-ln- heptyl-3-cyano-4-methyl-6- hydroxypyridone-2 ln-decyl-3-cyano-4-methyl-6- hydroxypyridinone-2 ln-dodecylol-3-cynano-4-methyl-6- hydroxypyridone-2 ln-octyl-3-cyano-4-methyl-6-hydroxypyridone-2 - 55 - - "- - 55 - —55 ~ -" - - "- ln-octyl-3-cyano-4-methyl- 6-hydroxypyridone-2 - "- -" - - "- -" - - 55 - - "~ - 55 - - 5, ~ ln-octyl-3-cyano-4-methyl-6-hydroxypyridone- 2 - 55 - - 55 - - 5, - -, 5 ~ - 55 - - 55 - - "- -" - - 55 - - 5, - 55 55 ln-octyl-3-cyano-4-methyl-6- hydroxypyridone-2 55 JJ 55 55 55 55 55 JJ Shade 4 yellow-green yellow-red yellow-yellow elons orange yellow-green - »- -» - yellow-red "yellow-green -" - - "- -» - - "- 55 -" - - "- yellow-red yellow-green yellow-green -" - - "- -" - - "- yellow-green yellow-red -" - - "- -" - - "- yellow-green -" - yellow yellow-red amber PL

Claims (2)

Zastrzezenia patentowe 1. Sposób wytwarzania barwników monoazo- wych nierozpuszczalnych w wodzie, stanowiacych jedna z mozliwych postaci tautometrycznych zwiazków o ogólnym wzorze 2, w którym A2 o- 65 znacza rodnik fenylowy podstawiony grupa nitro¬ wa, cyjanowa. trójfluorometylowa lub grupa o wzorze S02R3, -CONR4R5 lub -COR3 i który ewen¬ tualnie jest podstawiony jedna lub dwiema gru¬ pami nitrowymi, cyjanowymi, nizszymi rodnikami alkoksylowymi ewentualnie podstawionymi grupa84 012 wodorotlenowa lub acylóksylowa, lub nizszymi rodnikami alkilowymi lub fendksylowymi, przy czym R3 oznacza rodnik alkilowy, cykioalkilowy, arylowy lub aralkilowy, R4 oznacza atom wodoru lub rodnik alkilowy, cykloalkilowy, arylowy albo aralkilowy, R5 oznacza atom wodoru lub rodnik alkilowy, a Z2 oznacza rodnik alkilowy o co naj¬ mniej 5 atomach wegla, znamienny tym, ze ami- 8 ne o ogólnym wzorze A2-NH2, w którym A2 ma wyzej podane znaczenie, poddaje sie dwuazowaniu i wytworzony zwiazek dwuazowy sprzega sie ze skladnikiem biernym o ogólnym wzorze 3, w któ¬ rym Z2 ma wyzej podane znaczenie. 2. Sposób wedlug zastrz., 1, znamienny tym, ze stosuje sie skladnik bierny o wzorze 3, w którym Z2 oznacza rodnik alkilowy o 5—12 atomach wegla. i-n.n —rj5^!—x „0AA0 WZÓR 1 A-N-N WZÓRClaims 1. A method for the production of water-insoluble monoazo dyes, which are one of the possible tautometric forms of the compounds of the general formula II, in which A2 is a phenyl radical substituted with a nitro group, cyano. trifluoromethyl or a group of the formula SO2R3, -CONR4R5 or -COR3 and which is optionally substituted with one or two nitro, cyano, lower alkoxy or optionally substituted with a hydroxyl or acyloxy group, or with lower alkyl or fendxyl radicals is an alkyl, cycloalkyl, aryl or aralkyl radical, R4 is a hydrogen atom or an alkyl, cycloalkyl, aryl or aralkyl radical, R5 is a hydrogen atom or an alkyl radical, and Z2 is an alkyl radical of at least 5 carbon atoms, characterized by Amines of the general formula A2-NH2, in which A2 is as defined above, are diazotized and the resulting diazo compound is combined with the reactive component of the general formula 3, in which Z2 has the meaning given above. 2. The process according to claim 1, characterized in that the inert component of formula III is used, in which Z2 is an alkyl radical with 5-12 carbon atoms. i-n.n —rj5 ^! - x "0AA0 PATTERN 1 A-N-N PATTERN 2 . va/i», m |K OU^ Errata Tablica: rubryka 3, wiersz 22 w nózkach J"est: l-n-dodecylol3-cyjano-4-metylo-6- powinno byc: l-n-dodecylo-3-cyjano-4-metylo-6- LZG Zakl. Nr 3 w Pab., zam. 64G-76, nakl. 110+20 egz. Cena 10 zl PL2. va / i », m | K OU ^ Errata Table: box 3, line 22 in J legs" est: ln-dodecyl-3-cyano-4-methyl-6- should be: ln-dodecyl-3-cyano-4-methyl -6- LZG Zakl. No. 3 in Pab., Res. 64G-76, printed. 110 + 20 copies. Price PLN 10 PL
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GB1521534A (en) * 1975-03-25 1978-08-16 Ici Ltd Process for the colouration of aromatic polyester textile materials
IT1115389B (en) * 1976-08-25 1986-02-03 Ici Ltd DISPERSION AZOIC DYES, STABILIZED
DE3012863A1 (en) * 1980-04-02 1981-10-08 Cassella Ag, 6000 Frankfurt DYE MIXTURE, METHOD FOR THEIR PRODUCTION, DYES CONTAINING IT AND METHOD FOR COLORING AND PRINTING SYNTHETIC, HYDROPHOBIC FIBER MATERIAL
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