CS202534B2 - Method of producing water soluble azo daes of 2,6-diamino pyridine serie - Google Patents

Abstract

Water sol azo dyes of the 2,6-diaminopyridine series which in the free acid form have the formula: where D is the residue of a diazo component, E = H, opt. subst. alkyl or phenyl, Z = CN or carboxylic amide gp., R = H or opt. subst. aliphatic, araliphatic, cycloaliphatic or aromatic grp. or two grps. R together with the N atom form a satd. heterocyclic ring and n = 1, 2 or 3. The dyes have yellow to reddish blue tints and are esp. useful for dyeing natural and synthetic polyamides such as wool, silk, polycaprolactam and nylon, 6,6 in fast shades with excellent light resistance.

Description

The present invention provides a process for the preparation of dyes which, in the form of free acids, correspond to the general formula I in which:

(AND)

D means the rest of the diazocomponent,

E represents a hydrogen atom, a C 1 -C 7 alkyl group, a phenyl group or a methylphenyl group,

Z is cyano or carboxamido,

R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be interrupted by oxygen atoms and substituted by a hydroxyl group, an acyloxy group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, cyano, cyclohexyloxy, phenylalkoxy having I up to 2 carbon atoms in the alkoxy moiety, a phenoxy or tolyloxy group, optionally a hydroxyl, chlorine, hydroxyethyl, chloroethyl or C 1 -C 4 alkyl substituted C 5 -C 8 cycloalkyl or C 7 -C 15 polycycloalkyl group carbon, aralkyl having 7 to 15 carbon atoms, optionally hydroxysulfonyl, chloro, hydroxy, methoxy, ethoxy, methyl, ethyl, hydroxyethyl or hydroxyethoxy substituted

Phenyl, allyl,. C 2 -C 6 -alkyl or C 2 -C 6 -carboxyalkyl, or two radicals R 2 may form a pyrrolidine, piperidine, hexameethyleneimine, moofoline or N- meehhlpiperazine ring and.

n has a value of 1, 2 or 3, characterized in that the diazo compounds of the amines of the general formula (I) are:. · DNH ₂ are reacted with couplers · komppoanaami 'of the formula

E

(II) in which the formulas D, E, R and Z are as defined above, wherein the group or groups SO 4 H may be present in both residue D and residue R.

Alternatively, the dyes of the present invention can be prepared by forming compounds of the formula.

E

wherein D, E, Z and R are as defined above, are screened.

The monovalent radicals R may be the same or different.

Suitable radicals R @ 1 include, in addition to hydrogen, C1 -C8 alkyl groups which can be interrupted by oxygen atoms and can be substituted by hydroxyl, alkoxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aryloxy groups. optionally hydrogenated groups, chlorine atoms, hydroxyalkyl groups, chloroalkyl groups, or alkyl groups which are substituted. C 5 -C 15 cycloalkenyl or C 5 -C 15 aralkyl radicals, C 7 -C 15 aralkyl radicals or, optionally, hydroxysulfomyl groups, chlorine atoms, hydroxyl, alkoxy, alkyl, heterocyclic or hydroxyalkyl groups having a substituent content. Some phenyl radicals, as well as alkenyl, pyrrolidinyl allyl and carboxyalkoxy. remnants. »‘

Leftover D diazocomponent with drain! In particular from aniline, aminnotalimide and aminoazobenzene derivatives which may be substituted by, for example, hydroxylsulfonyl groups, atoms, halogen, alkyl, alkoxy, acylamino, cyano, alkylsulfone, phenylsulfone, nitro, carboxyamide, alkoxyl, carboxamide, alkoxyl, alkoxy carboxamido-, tetraphthamido-, N-sulfo-4-trifluoromethylsulfonamido- or benzthiazolyl groups.

Exemplary polymers in addition to the substituents listed above include, but are not limited to: chloro, bromo, methyl, ethyl, trifluoromethyl, methoxy, e-oxo, meetyl- and hydrocarbyl, methoxycarbonyl, ethoxycarbonyl, beta-ethoxy ether -methoxyxalkoxycarbonyl, buhoxylcarbonyl, beta-butoxyethoxycarbonyl,--methyl-, n -ethyl-, opyl-propyl-, N -butyl-, Ν-hexyl-, N-biala-ethylhesyl-, i-ieta-hexethoxylemethyl- , N-gammamethooylrotylcarbtxamido,

N, N-dimethyl-N, N-diethyl-, N-methyl- N -beta-hydroxy-ethyl-, N-phenylcarboxamido, piperidocarbonyl, mono-pyrrolidocarbonyl or pyrrolididocarbonyl, as well as the corresponding sulfonamino-thio-thio-thio-thio-thio-thio-amino, acetylamino-thio-thio-thio-amino; , methylsulfonyl amino, phenylsulfonylamino, hydroxyasethylamino, benzoylamino, p-chlorobenzoilalamino, lenacetylamino octpint, as well as residues of the formulas -N-CO-CH, -N-HO-CHCl, -N-CO-CH- or -N-CHO.

I I II

CH CH, COHKCH

3 2 53

Residues in the meaning of the symbol R are, for example:

in addition to the residues listed above,

1) optionally substituted alkyl radicals, such as:

CH ^ H ^ ₂ H, n- or i-CY ^, n- or i- ^ Hg, C ^ H ^,

CH ₂ -CH-C ₄ H ₉ , CH ₂ CH ₂ OH, (CH 2) ₃ OH, CH ₂ CHOH, ^C 2 ^H ₅ CH ₃

CH-CH ₂ OH, (CH 2 OH, (CH ₂ ) ₆ OH, СН- (СН ₂ ) зС (СНз) ₂₎ (CH ₂ ) ₂ 0 (CH ₂ ) ₂ 0H, (СН ₂ ) зО (СН ₍₂ ) 4ОН ^:

CH ₃ CH. OH (CH 2) ₃ OC ₂ H ₄ OH, (CH 2) ₃ OC ₂ H ₄ OCH ₃ , (C ₁ O ₃ OC ₂ O ₄ O,

(CH ^ OC ^ OCgHg, (CH ^ OCH-CHgOC ^, (СН ₂ ) for <0СНСН ₂ 0С4Н ₉ , (СН ₂ ) for <0СН ₂ СНОСНз, (СН ₂ ) for <0СНСН20С ₂ Н ₅ ,

CH3 CH. CH3CH.

corresponding residues in which the grouping -OC ₉ H.-, -OCH-CH- or -ОСН-СН is present, - two are present |

CH3CH kr & t, three or four times, longer. ΗΗ ₂ ΟΗ ° ΟΗΗ _3, C = H ^CH H ^ ^{<^} 2 ^H 5 ^I CH ₂ CH ₂ OO ₆ Hh »(HH ₂₎ 3OCH3, (НН ₂ 1 ₃ 2Н ₂ Н ₅ (HRH) J2C ₃ H ₇ , (HH ^ OC ^ g, (HH ^ OC ^ CHC ^ g,

C 2 H ₅ (CH ₂₎ .J C6H131 ^{O (C} H 2) ³ C ₈ H ₁₇ ^(CH2> 3 ^O - <H) ₍₂ СН) _з0С б Н ₅ -CHCH ₂ OCH3 ,. CHCH ₂ OC4Hg, 'CHCHgOCgHg,

CH. CH3 CH.

, (CH 2) 3 OCH ₂ C ₆ H ₅ , (CH 2) 3 OC ₂ H ₄ C ₆ H ₅ , СНСС _о 0СС "С, Нс, CH" CHOCH ", CH-CH-OC-Hc, | ²² 6 ⁵ 2 3 2 2 5 '

CH 3 H 3 C CH 3

CH ₂ - (H 2 -CH ₂ CH, (CH ₂ ) ₂ CN, (CH ₂ ) ₅ CN,

2) optionally substituted cycloalkyl and polycycloalkyl radicals, such as:

~ C. - (h), _ / 'hj,,

· XCC -CO '<x>'

?

OH ^ 3> - ^{ch 2c} ',

-Ш ·

»

OH - Q - <H, OH>

ж>

CH 2 CH 3 QH,

OH ', as well as the corresponding radicals containing, instead of the C 1-4 H group,

3) aralkyl radicals such as:

CHCH-CH

I ² CH3

^C H group СдНдСНз;

(4) optionally, a substituted phenyl moiety such as:

С _б Н ₅ , С _б Н ₄ СНз, С ₆ Нз (СНз) _2> С ₆ Н ₄ ОСНз, C ₆ H ₄ OC ₂ H ₅ , C ₆ H ₄ OH, C ₆ H ₄ NH, C ₆ H ₄ OCH ₂ CH ₂ OH or CH ₄ Cl; . COCHj

5) CH ₂ CH = CH ₂ . (CH 2 O, OOO, ^(CH 2 COOH and ^{(CH 2} n- ¹

O, where n = 2, 3, 4 or 6,

C2H OCOCIH3 _4, C 2 H ₄ OC (O C2H4OCOCH2COCH3, COC ^ H ^ ^ (H2H4O) 2 CHO, (CH2) 3OCOCH3, (H¾) зOCHO,

₄ C 2 H ₄ COOH OCOC2H. '' ”

The sulfone groups contain residues as defined by the symbol. R is, for example, the radicals of the formulas: CH ₂ CH ₂ SO ₃ H, CH ₂ CH ₂ OSO ₃ H, (CH ₂ ) ₃ OSO ₃ H, CHoCHOSO-jH, (CH ₂ ) ₄ OSO ₃ H, (CH ₂ ) ₆ OSO ₃ H, <2 H - (<3 H ₂ )) C ((1 H ₃ ) ₂ ,

CH3 CH ₂ OSO ₃ H (CH 2) 2 O (CH 2) 2 OSO ₃ H, (CH 2) ₃ O (CH 2) 2 OSO ₃ H, (C ₁ H 2 OO ₂ H 2 OO ₂ H, (CH 2) ₃ OC ₂ H ₄ OCH ₂ CgH ₄ SO ₃ H, ₃ OC2H4OC2H4HнH4SO ₃ H · (C ^) ₄ 3OC2H OCgH ₄ SO3H, CH2CH2OCgH4SO3H (0¾)

CH.OSO3H,

CH.CXH.SO-H CH

O — C ₂ H ₄ OSO ₃ H,

CH.SO.H, (CH2) 3OCH2CgH ₄ SO3H, (H¾) ₃ O4 ( ₄ CgH ₄ S4 ₃ H ₎ СННСНСсННО ^ J), · CHj

C2H4OSO3H, ₃ h

OC.H ₂ CH ₂ OH

SO3H

C ₆ H ₄ OCH ₂ CH ₂ OSO

CH ₄ OSO, H

Preferred substituents for R include: hydrogen atom and radicals of the formulas, CH3, C 2 H _5, n- or 1-0¾¾. n- or 1-0 ^ 1 ,, CGH, 3, C ^ C ^ OH., _(CH2) j0H, CHgCHOH, (^ H ^ OH ^•..!. CH ₂ (CH 2) ₆ OH, СН ( СН2) ₃ С (СНз) 2, (CH 2) ₂ O ( 'CH _{2) 2} Oi (0¾) jOCC JgOH ^ (C ^ O ^^ OH

CH3 OH

^OH - (CH ₂ ) _-N (n = 2, 3, 6), CH ₂ CH ₂ OCH ₃ , (CH ₂ ) ₃ O (CH ₂ ) ₆ OH,

СНССИ-к

I ²³ and ₃

CH (CH ₂ ) ₃ - CH ₃ ch ₃

>

(CH ₂ > ₃ O

><CH ₂ ) ₂ O

, (CH ₂ ) ₃ OC ₂ H ₄ OCH ₃ , (CH ₂ ) ₃ OC ₂ H ₄ OC ₄ H _g , (CH ₂ ) ₃ OC ₂ H ₄ OC ₆ H ₅ ,

'OO' ΌΟ ^{'CW5, СгН4СбН5, сн} 2 ° ^{нс б н} 5 \ ^CK 3 CH ₂ CH ₂ CHC ₆ H _5, C ₆ H ₅ C ₆ H ₄ CH _3, C ₆ H ₃ (CH _{3) 2,} C ₆ H ₄ OCH ₃ , c ₆ h ₄ oc ₂ h ₅ , c ₆ h ₄ oc ₂ h ₄ oh, CgH ₄ Gl ·,

CH ₃

CK ₂ CH ₂ SO ₃ H, CH ₂ CH ₃ OSO ₃ , (CH ₂ ) ₃ OSO ₃ H, CH ₃ CHOSO ₂ , (CH ₂ ) ₄ OSO ₃ H, (CH ₂ ) ₆ OSO ₃ H, (CH ₂ ) ₂ O (CH ₂ ) ₂ ^GH 3 axis ₃ H, (CH ₂ ) ₃ O (CH ₂ ) ₂ OSO ₃ H, (ch ₂ ) ₃ o (ch ₂ ) ₄ axis ₃ h, (ch ₂ ) ₃ o (ch ₂ ) ₆ axis ₃ h _{(CH2) 3} oC ₆ H ₄ to ₃ H, (CH _{2) 3} OCH ₂ C ₆ H ₄ SO ₃ H, (CH _{9) 3} oC ₂ H ₄ CGH ₄ SO ₃ H, CH ₂ C ₆ H ₄ SO ₃ H, C ₂ H ₄ C ₆ H ₄ SO ₃ H, CH ₂ CHC ₆ H ₄ SO ₃ H,

CH ₃ , c ₆ H ₄ so ₃ H,

CH ₃

SO ₃ H

och ₃

SO ₃ H

Cl

5О ₃ М

The dyes of the above general formula (I) can be obtained or used in the form of the free acids or conveniently also in the form of water-soluble salts, for example in the form of alkali, ammonium or substituted ammonium salts. Substituted ammonium cations in these salts are, for example, trimethylammonium, tris-beta-hydroxyethylammonium, methoxyethylammonium, hexyloxypropylammonium or dimethylphenylbenzylammonium cation.

The diazo compound of the amines of the formula II can be used for the preparation of dyes of the formula I

D-HH ₂ (II) is reacted with the coupling components of formula III

(III) wherein normally either residue D and / or the compound of formula III contain at least one sulfo group. Diazotization and coupling are carried out by methods known per se. However, the novel dyes according to the invention, in particular dyes containing a group of semi-esters of sulfuric acid, can also be obtained by first preparing the corresponding non-sulfo-containing compounds by diazotization and coupling and then treating the intermediates with sulfoic agents such as concentrated sulfuric acid, olea are converted into dyes of the general formula I. Details of these processes are given in the examples.

As . compounds of formula II include, for example:

aniline, 2-, 3- O 4-chloroan-10-ol. 2-, 3- F ^ опОИо, 2-, 3- O 4-nitrophenyl 2 ’, 3- O ^ tol ^ dto, 2-, 3- O 4-cyifiool,

2.4- dikyannnOlio,

3,4- or 2,5-dichloroaniline,

2.4.5- trichltranilio, ‘

2.4.6- ^^ УЮгооШо,

C-chloro-4-nitroaniline, '

2-orom44onitroonin, '*

2-kaoo-44o _n itrooniOin, '

2-meeiylsulloo01-44n0troaa01io,

4-CH1 □ □ _{-2-n0troon01io>.}

4-methyl-42n0irooa01io,

2-Methyl-4-nitroooO10, '

1- OIninoo42- _Γ ifluormethyl 4-chlorbenzeo,

2-chloro-54omiao0eaooat0ril, ·

2-ooiaOo4-4Cl-chloro-azitrile, o-butylamide or 1-amino-n-nitrobosyl-4-sulfonic acid alpha-methoxyethylamide,

140minobenoeno4- oeehhlsulfon _1,

_1-aminoo2> 6 ~ dibrombenzzn 4_methylsulfoni

Ainiaoo- _1-> 6-4-dichlorbeozeo meeiwlsulfon ,.

methyl ester, propyl ester, tert-oethoethylthiyl tert -butyl ester of 3,5-dichloroothrooilic acid, εζζ^^Ιααα ethy ethy, ethyl-, o- or isoproppleether o- or o -tta-methylhexyl tert-3,5-dibromannhyanilic acid, -p-phenylenediamine,

N-acetyl-m-phenylenediamine

N-benzymphonyl-β-phenylenediamine, 4-aminoacetophenoate.

4- or 2-oeinobéosenoeno,

2- o 4-Amino-phenylsulfoo, m-ethyleneSr, ethyl ester, propyl ester, methyl ester, beta-oilyl ester, beta-o-methylhexyl ether, bet-t-oxylthyl ester, methylddglyl20ethereroligig220oestestetrol

2-, 3- or 4-η 4 -ioioozoic acid,

3- or 4-aminofi-8-acid, dimethylaminoethyl diethyl ester, diproppyester of dibutyl 5-amino-o-phthalic acid, dibutyl ester or amino-o-terephthalic acid, amd, mmylmethyl, propylamide, butylamide, isobutylamide, cyclohexylomide, beta-ethylplomide or ioioobozoic cpselioy, dimethylamide, diethylemide, pyrrolidide and moofolide of 2-, 3- or 4-omobenzoic acid, 5-ainoinoosophthalic acid diamide, imide, beta-hydroxyethylimide, methylimide, thylimide and tolllioid of 3 or 4-aminootalimide, dimethylamide ditthllaeid, pyrrolidide o moofolide 4-amino-4-amino-4-amino-4-amino-4-aminoacid;

3- or 4-aminophthalic acid hydrazide, thiophide, butyl amide, and mt-4-aminophthalic acid;

1-aeinoan0rachinoo ,.

'4-Aminodiphenylene oxide,

2-aminobenzthiazole, 4- (4-nitro-4-thylaminium); '

4-4miňb4Zbenizni,

22.3-O-methyl-4-amino-4-benzoyl,

3,2-dimethyl-4-amino-4-benzene,

2,5-Oimethyl-4-amine-4-benzene,

2-methyl-5-methyl-4-methylbenzene,

2-Methyl-4 ', 5-O-methoxy-4-4-mercurybenzene; c ^ É ^ 2 ^ c ^ enizni,

4 'lithium-2-methyl-methoxy-4-methoxybenzyl,

4 ^/ -chloг2 - monk-444mminoazoeelzel,

2.5- Oimethhxy-4-4milb4Zbenlznl, ^{4'-ocУlor22,5} dimtihoyy-04eminoazoeenzel, _{'-iitbo-2,5-dimeihoyy44-l, m} and _n QazbeelZel,

4'-chloro-2,5-dimethyl-4-amino-4'-methoxy-2,5-dimethyl-4-methyl-4-zobenzene,

4 * -lith-40 ~ øiinoazoeelzel

3.5- 0ieгom-4o4milh4zhenlznl,

2,3 - Oichloг-04amino4zpeelzel,.

3- menoxy'4o4milh4zb.enlznl,

1-ailinobeniene-2-, -3-inbb -4-sulfonic acid,

1-amino 2,4-inbb 42 _J 5-0 -oulonic acid,

1-4mino-24-methylbenzene · 44-sul: bonovhu acid,

1-amino-3-: methylbenzene-4-sulfonic acid;

1-4mino 4-menhylbenzen ^ - inbb O35 _S ulfonovhu acid

2o _; thread4lio45-зulhlho, vhu. acid,

4-nitrenili025-Sllhl's acid,

2-cУioranilil44o nnbb 554 _SU lfonic acid,

3-chlorophenin-.alpha.-sulfonyl acid,.

4-Chloro-4-ynyl-2-sulfonic acid,

1o4mino-3,4o0ichlc) benzene565sulfonic acid,

-4mino-2,5-0-chlorobenzene-4-silfdolic acid,

154minOb4-menthУ-5-chlorotheenzel52-oulphoric acid,

1- 4minc) bЗ-IeentLhУ-4-chlorothieno-6-ounonic acid,

2- 4Ieino-4-4OulfobeilzhhvhU acid, t 1-4mil0-44o4cntamllbeenzene-2sulphuric acid,

-4mino-5 · 44-tetramilbeenzene-2ooslfonic acid, 4-amino-2-mannyl-4o: ttobelzen-5ooslfonic acid,

1-4minoenlУr4chilhlo2ooslhonic acid,

1- 4Iiinihl4lelel525 mbo o4ooulhonoVhu acid,

2- 4И1П1М! 4и4 en-1 -oulphenoic acid as well as * Oiazocomponent formulas:

HO ₃ S

HO ₃ S

HO ₃ S

HO ₃ S

I 1

HO ₃ S

₂ nh ₂

ho ₃ so

Cl

HO ₃ S — о — H ₄ C ₂ -

nh ₂

Cl

NH

HO ₃ S — O — H ₄ C ₂ —o сн _э

3 or

НО ₃ 5-О — Н ₄ С ₂ -

The dyes of the general formula (Ib) are of particular technical interest

(Ib) wherein d 'is a radical of formula or

of'

Y is cyano or carbamoyl, is hydrogen, cyanosapine, chlorine, bromine, methyl-sulfonate, ethylsulfonate

Si-phenylsulfone, alkoxycarbonyl or sulfo, represents a hydrogen, chlorine or bromine atom, or sulfo, is hydrogen, chlorine, bromine, methyl, alkoxycarbonyl, 2'-benzothiazolyl or sulfo,

X represents a hydrogen atom, a methyl group, a methoxy group or a sulfo group, χ nebo represents a hydrogen atom, a methyl group, a methoxy group or a sulfo group, o '

X is hydrogen, methyl or methoxy, m is 1 or 2,

T is hydrogen or substituent a.

R is as defined above.

A preferred radical for Z ¹ is cyano.

Preferred T moieties are alkyl groups having 2, which may be interrupted by oxygen atoms and substituted by hydroxyl or OSO4H groups, further benzyl, sulfo, phenylethyl, sulfo-substituted phenylethyl or phenyl, optionally substituted with sulfo and / or other residues.

up to -8 carbon atoms, groups, phenoxy-substituted benzyl

The radicals ^GH 3> ^G 2 ^ 5 ' ^G 3 ^H 7 * within the meaning of the symbol T include, for example, the radicals of the formulas: с ₄ н ₉ , с ₂ н (сн ₂ ) ₃ сн ₃ , сн ₂ сн ₂ он, с ₆ н ₁₃ , (сн ₂ ) ₃ он, ch ₂ ch ₂ and ₂ ch ₂ oh, ^C 2 ^H 5

CH ₂ CH ₂ OC ₆ H ₅ , CH ₂ CH ₂ OSO ₃ H, (CH ₂ ) ₃ OSO ₃ H, CH ₂ CH ₂ OCH ₂ CH ₂ SO _{3 3} , ₍ H, CH ₂ C ₆ H ₅ , ch ₂ c ₆ h ₄ s ₃ h, c ₂ H ₄ c ₆ H ₅ , c ₂ h ₄ c ₆ h ₄ s ₃ h, c ₆ h ₅ , c ₆ h ₄ s ₃ h,

_n ebo._W ^N ° ^3H '

Preferred R radicals in the dyes of the formula I are C 1 -C 8 alkyl groups which can be interrupted by oxygen atoms and substituted by hydroxyl, phenoxy, benzoyloxy or OSO ₃ H groups, furthermore benzyl, phenethyl, sulfo substituted benzyl or phenethyl an optionally substituted phenyl or hydroxysulfopropylphenyl group, or a hydrogen atom;

The SO ₃ H groups are preferably present either in only residue D or only in residue D. R, especially when R contains a phenyl radical. ,

Preferred diazo components are, for example:

2-, 3- and 4-aminobenzoic acid methyl ester, ethyl, α- and isopropyl ester, and 2-amino-3,5-dichlorobenzoic acid methyl ester, ethyl ester and isopropyl ester, 2-amino methyl ester, ethyl ester, and beta-methoxyethyl ester -3,5-dibromobenzoic acid, 3-bromo-4-aminobenzoic acid ethyl ester, aminoterephthalic acid diethyl ester,

2-aminobenzonitrile,

2,4-dicyananiline,

2-amino-5-chlorobenzonitrile,

2-amino-5-bromobenzonitrile, amino-3-bromo-5-chlorobenzonitrile,.

2-amino-3,5-dibromobenzonitrile,

2-amino 3,5-dichlorobenzonitrile,

2-amino-: - trifluoromethylbenzene,

2-Amino-5-chlorotrifluoromethylbenzene

4-aminobenzene-1-methylsulfone,

3-chloro-4-aminobenzene-1-methylsulfone,

2-aminodiphenylsulfone,

4-aminodiphenylsulfone, ⁴ -beta-hydroxyethylimide of 3- and 4-aminophthalic acid, beta-methoxyethylimide of 3- and 4-aminophthalic acid, butylimide and tolylimide of 3- and 4-aminophthalic acid,

1-amino-4-nitrobenzene,

1-amino-4-acetylaminobenzene,

1-amino-3-acetylaminobenzene, 4-aminobenzoic acid amide,

4-aminobenzoic acid N-methylamide, N-butylamide and N-beta-ethylhexylamide,

4-aminobenzoic acid Ν, Ν-diethylamide, 3- and 4-aminobenzenesulfonic acid amide,

3- and 4-aminobenzenesulfonic acid N-butylamide, 3- and 4-aminobenzenesulfonic acid morpholide,

2-chloroaniline-4- or -5-sulfonic acid,

3-chloroaniline-6-sulfonic acid,

4-chloroaniline-2-sulfonic acid,

1-amino-3,4-di-chlorobenzene-6-sulfonic acid,

1-amino-2,5-dichlorobenzene-4-sulfonic acid,

-amino-2,5-dibromobenzene-4-sulfonic acid,

1-amino-4-ethyl-5-chlorobenzene-2-sulfonic acid,

-amino-3-methyl-4-chlorobenzene, n-6-sulfonic acid and amines of formulas

HO ₃ S

СН ₃

Preferred coupling components are, for example, compounds of the formulas:

C ₂ H ₅

CH ₃ _conh ₂ χχ hn-^ n ^ nh-c ₂ h ₅

C ₂ H ₅

CONH.

Η — N

СдНд (п)

₆ and ₅

н ₂ н

CN

NH — C ₄ H ₉ (n)

сн ₂ ~ сн ₂ ~ сн ₂ —ОН

сн ₂ —сн ₂ —о-сн ₂ ~ сн ₂ —он

CN

NH — CH ₂ —CH ₂ —O — CH ₂ —C Η 2 — O Η

C ₄ H ₉

C 4 H ₉ (n)

NH — CH ₂ —CH ₂ —CH ₂ —O — SO ₃ Na CH ₂ - CH ₂ —СН ₂ - О — SO ₃ Na

AND

where r · '' _r

R = (CH _{2) 2} OH. (CH ₂ ) ₃ OH, (CH ₂ ) ₂ 0 (CH ₂ ) ₂ 0H, (CH ₂ ) ₃ 0 (CH ₂ 1 ₄ 0H

CH.

CN

-J-н у hh (CH _{a) 2} -O-CH _third CH ^- —o

Í ^{H1 cn}

HN ^N 'NH— (CH2) a — OCN3 (C ^H2 ) and —O— (CH _a ) _and —OH

CH, CC

-N 'NH- (CH _a ) ₃ —OCH ₃ (CH _a ) _and —O— (CH _a ) _and —OH

XX

H N N 4 NH-CH ₃ -CH ₂ -O ^H CH ₃ -CH ₃ -OH

The novel dyes of the invention are yellow to yellow. reddish blue and suitable for coloring natural. and synthetic polyemias such as wool, silk, nylon 6 or nylon 6,6. When these dyes are ingested, brilliant dyes are obtained with excellent fastnesses, in particular fastness to fastness. light. Also the solubility of some of the dyes is excellent.

The invention is illustrated by the following examples which do not limit the scope of the invention in any way. Unless otherwise indicated, parts and percentages are by weight.

Example 1

122 parts of the product of the reaction of aniline with 2,6-dichloro-3-cyano-4-methylpyridine (1: 1, melting point 135-140 ° C) is refluxed for 5 to 9 hours with 450 parts of n-butylimine, then the excess butylamino is distilled off as much as possible, the hot residue is stirred with about 1500 parts of ice water and the mixture is acidified with hydrochloric acid to a pH of about 1 to 3. The precipitate formed is filtered off, washed with water and dried. I44 parts of a colorless product having a melting point of 115 DEG C. are obtained, which are introduced in portions into approximately 450 parts of 23% olea at normal temperature in portions. The sulfonation mixture was stirred at 30-40 ° C for 3-4 hours, then about 1,500 parts of ice, 500 parts of saturated sodium chloride solution and finally 400 parts of 50% sodium hydroxide solution were added. The reaction mixture is stirred overnight, then cooled to about 5-10 ° C, the precipitated product is filtered off, washed with sodium chloride solution and dried. About 120 to 130 parts of a colorless powder product of the likely formula are obtained

HH-C ₄ H _q (n) containing less by-product of the probable formula

In about 60 parts of water and 12 parts of 30% hydrochloric acid, 6 parts of anthranilic acid methylstyride are dissolved, 60 parts of ice and 13 parts of 23% sodium nitrite solution are added, the mixture is stirred for 30 to 45 minutes at 0-5 ° C, then, if desired, the excess nitric acid excess is decomposed in the usual manner, and the resulting mixture containing diazonium salt is added to a solution or suspension of the sulfonated coupling components described above, in about 400 parts. water and 10 parts of 30% hydrochloric acid, cooled to 0-5 ° C. The mixture is stirred for 30 minutes at 0-5 ° C and sodium acetate solution is added until the pH reaches about 3. After completion of the coupling, about 50 parts of sodium chloride are added and the mixture is stirred for about 2 hours. probable formula

NH-C ₄ H _qn )

SO ₃ Na oddilirujs · After drying about 20 parts of an orange-red powdered product are obtained, which in water swells into an orange-colored solution and dyes the polycaprolactam fabrics in bright, deep golden-yellow shades with very good fastness.

The dye described above dyes the wool in a golden yellow tint.

Example 2

14.3 parts diazocomponent formula

202534 24 is dissolved in a mixture of 150 parts of hot water and 6.5. 13 parts by volume of 23% sodium nitrite solution are added thereto, and the mixture is poured into about 200 parts of ice and 25 parts of 30% hydrochloric acid with stirring. After about 4 hours of stirring at ^0-5 ° C the diazotation is dancing. ^p řípadnS at present for the ^{p ic} acid tek ^d ^ a ^ ^é it. is canceled and Uvyklým manner к mixture Rida ^P at ¹⁰ ° C, cooled ^to 9.5 parts mites coupling com ^p · onenty formula

CHj-CHj-CHj-OH is dried in about 100 parts of formamide, 10 parts of 30% hydrochloric acid, and 0.5 parts of an emulsifier. The pH of the coupling mixture is adjusted to about 4 with 50% sodium vinegar solution. After the coupling, the dye formed is precipitated by the addition of about 100 parts of potassium chloride and filtered off. After drying, 20 parts of a dark powder product of formula / О3К H ₃ C ^$ 3 CN ^KO ~ ^^ - ^{N == N} - ^^ - ^N = N-N ^H-ZS -

NH-CH-CH-CH ₃ OH in water which cleave to reddish purple color solution and dyes fabrics of polykap ^ Ia ^ emu in bluish red shades. with very good constancy.

By analogy to Examples 1 and 2, dyes can be prepared as summarized in the following table, where they are characterized by an influx of diazo components. and copulation components:

Example Diazocomponent number

Coupling component

The color shade on the polylactic lactam

^R 1 = · -C ( ⁵ r ₂ = -c ₃ ) red bluish red red

Example Diazocomponent number

Coupling component

Color shade on polycaprolactam

R ₁ = -CH ₂ -CH-C ₆ H ₅ red ch ₃ r ₂ = -C ₂ H ₄ -OH

R 1 = -C 8 H 2 red ^R 2 ⁼ - ^CH 2 ^CH 2 ^{O CH} 2 ^GH 2 ^OH

R | = -C (H (Cn) bluish)

R ₂ = - (CH _{2) 2} -O- (CH _{2) 2} -OH red

bluish

Red bluish

Red r ₂ = -ch ₂ -ch ₂ -ch ₂ -.oh

SO ₃ H ¹¹ HO ₃ S - ^^ - Ν = Ν - θ - NH,

^R 1 ⁼ -CH ₂ -CH ₂ -CH ₂ -O-CH ₃ red r ₂ = -ch ₂ -ch ₂ -o-ch ₂ -ch ₂ -oh

R 1 = -CH ₂ -CH ₂ -O-COCH ₃ red r ₂ = -ch ₂ -ch ₂ -ch ₂ -ch ₃

R ₁ = - (CH,) ₃ - О — СН, —СИ, —O — ζ-y bluish

r ₂ = -CH ₂ -CH ₂ -OH red _ / л ^{Ri =} } = / red ocw ₃ ^{R2 =} -CH2CH3-CH2-OH

Coupling component i

Assign Diazocomponent Number

Color shade on polycaprolactam оси _э

CH ₂ -CH ₂ -CH ₂ -OH

-СН_-СН _Л -СН _Л -ОН bluish red red red red orange scarlet

22nd HO ₃ S - H = N - / - NH 3 ^R 1 ^{_ C} 2 ^H 5 Šarlato- R 8 = -CH ₂ -CH ₂ -O-CH ₃ you 23 HO ₃ S — XX-N = N-Xy-NH _a ^R 1 = -C ₂ H ₅ r ₂ = -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ OH Sarlatový 24 ^ho 3 ^s —C3 ^- * ^{NHj R} 1 ^{= C} 2 ^H 5 »л ΟΛ ΟΛ ΟΛ ΟΛ red

HO ₃ S — N = ^N ~ HH '

CH ₃

yellowish red

I - - ^C 2 ^H 5, = -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OH yellowish red

Žarlatový

Example Diazocomponent number

Coupling component

Color shade for polycaprolactam

^R 1 ^C 2 ^H 5 ^R 2 ⁼ ' ^GH 2 ~ ^GH 2 ~ ^O ~ ^SO 3 ^Na

Scarlet

CH ₃

R _1j2 = -CH ₂ -CH ₂ -O-CH ₃ ^R 1,2 ⁼ " ^C 2 ^H 5 ^R i -V4

R ₂ = -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OH ^R 1 ^{= -C} 2 ^H 5

R ₂ = -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OH ^R 1,2 ^{= C} 2 ^H 5 = CH ₂ -CH ₂ OH

R _1j2 = CH ₂ -CH ₂ -O-CH ₃ ^R 1,2 ⁼ (θ ^Η 2 ⁾ 3 '' ^Ο ' ^ΟΗ 3 scarlet

Scarlet scarlet

Red - Violet Burgundy Red - Violet Red - Violet Red - Violet

28 ^х

Example Diazokomponente number

Coupling component

Tint for polycaprelac • tamu

SOjH

0- =

R 2 = -OH ₂ -CH ₂ -OH červenofiaoový ^R] = ^C 2 ^H 5 ^R 2 = - ^C H2 ^C H2 ° ₂ -CH ₂ -CH -0H Červenom ^ - ^ AOC ^ v ^ y

červenofiaoový

SO ³ H ^R 1.2 = ^C 2 ^H 5 claret, 41

NH

Rj 2 = '- θβΗγ (η) claret

SO3H

parts of the dye of the formula ^{R 1} , ^-C 2 ^H 5 'r ₂ = -ch ₂ -ch ₂ -o-ch ₂ -ch ₂ -oh ^{R 1} = -c2 ^h 5

R ₂ = -C 1 -C 4 -OC 4 -C 4 -OH ^R 1 ^, 2 · = ^-C 2 ^H 5

burgundy burgundy, 29..202534, with vigorous stirring at room temperature, is introduced into 120 about 120 parts of 100% sulfuric acid. The mixture was stirred overnight at 20-30 ° C, then poured into a mixture of 500 parts ice, 100 parts 50% sodium hydroxide solution and 50 parts potassium chloride. After cooling to 0-10 ° C, the precipitated dye of formula - is precipitated. '

filtered, washed with dilute potassium chloride solution and dried. A reddish-brown powder product is obtained which dissolves in water into a yellowish-red solution and dyees the fabrics from polycapolk in yellowish-red shades with good fastness.

In an analogous manner to Example 45, coupling compounds containing esterifiolated sulfo groups as well as dyes can be prepared as summarized below:

Example

Dye number

Scarlet color shade

H ₃ C CH

-ХУ N == N ^ Χ- ^ΝΗ —CH ₂ —CH ₂ —O-SO ₃ K

NH-CH ₂ -CH ₂ -O-SO ₃ K

Scarlet

yellow

_{NH-CH2-CH2-CH2-O-SO 3} Na

golden yellow

COOCH

Br

CN H ₃ C r _N a

NH — SO3K yellow scarlet i

red-orange i

Example .53 parts diezocomponent formula

is dissolved in a mixture of 150 parts of water and about 6.5 parts of 50% sodium hydroxide solution, 12.5 parts of 2% sodium nitrite are added, the mixture is allowed to cool and. 150 parts of ice are added. The mixture cooled in this way to about 0 ° C was acidified by the addition of 16 to 18 parts of 30% hydrochloric acid. After about 2 hours, the diazotization is complete. . The swollen nitric acid is decomposed in the usual manner and the mixture containing the diazonium salt. A solution or suspension of 13.1 parts of the coupling component of the formula is added over 10 minutes

V, ZH ’

Qh ° ~ NH-CH 2 -CH ₂ -O-CH ₂ 'CH ₂ OH and 10 parts of 30% hydrochloric acid, 250 parts water, 0.5 part of emulsifier, and 150 parts of formamide, cooled to 0 ° C. the mixture is stirred for 15 minutes at 0 to 5 ° C, then the coupling is terminated by adding 30 to 50% sodium acetate solution until a pH of ca.

3.5 to 4.5. 150 parts of sodium chloride are added to the resulting mixture, the mixture is stirred for about 3 hours, after which the precipitated dye of the formula

filtered, washed with a slightly dilute sodium chloride solution and dried. 26 parts of a red powder product are obtained, which is melted in water to red. colored solution and dyes · polycaplakaem fabrics in scarlet red shades with excellent fastness.

The dyes mentioned in the following overview are prepared in an analogous manner to Examples 1, 2 and 53, characterized in that they are characterized by the corresponding diazo components and the coupling reactions.

Example Diazocomponent component number

Color shade

R, 2 · = -CH ₂ -CH ₂ —OH '-CH ₂ -CH ₂ -CH ₂ -OH-brilliant orange

Example number

Diazokomponenta

Coupling component

Color shade

r ₂ = -CH ₂ -CH ₂ -OH orange

R 1 = orange r ₂ = -ch ₂ -ch ₂ -o-ch ₂ -ch ₂ -oh.

R ^ = -C ^ H ^ (n) brilliant ^{R2 =} - • ^{: Н} 2 ~ ^СН 2 ' ^{О СН} 2 ^СН 2 ^_ОН orange

R ₁ = - (CH ₂ ) ₃ -O-CH ₂ -C ₆ H ₅ ^R 2 ⁼ " ^CH 2 ' ^CH 2" ^OH orange

^R 2 ⁼ -CH ₂ -CH ₂ -CH ₂ -OH

/ CJC / ¹ - ^{NHZ C%} H ₃ H Ao

^R 2 ⁼ -CH ₂ -CH ₂ -O-CH ₂ -gh ₂ OH R ₁ = -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ OH "2 ~ t) ^R 1 = -C ₆ H ₅

R ₂ = -C ₄ H ₉ (n) brilliant scarlet brilliant scarlet scarlet

brilliant yellowish red brilliant yellowish red yellowish

Red brilliant orange

R _{1 2} = -Cytin) brilliant orange

Diazocomponent Example

The coupling component

r ₂ = ~ ch ₂ -ch ₂ -gh ₂ -oh

^R 1 ^Rg

RG = C 4 H ₉ (n)

R = = ⁵ ° ^3Νβ _ H ₂ = C ₄ H ₉ (n)

R = ^ ^QT ° ^3Na

R ₂ '= C ₄ H ₉ (n)

-ΛΛc-Rjr ^-C4H9 (n)

R

SO ₃ Na

Color shade yellowish red yellowish red yellowish red orange orange

Scarlet

Scarlet Golden Yellow Golden Yellow Golden Orange

Example

Diazokomponenta

Cooulation component

Colored

shade

C

Pine

R _? = -CH ₂ -CH ₂ -CH ₂ -OSO ₃ Na

R,

R ₂ = -C 1 -C 4 -C 1 -OSO ₃ Na

R 1, 2 -CH ₂ -CH ₂

SOsNa orange orange

Scarlet golden yellow

R ₁ 2 = ~ ^CH 2 у golden yellow

CH 3 phi — K 2 ^SO 3 ^Na

R 1, 2 ⁼ —CH ₂ —CH ₂ —O 4 V. golden yellow

R ^ = ^ golden yellow -CgH ^R 2 = -CH ₂ -CH ₂ -G _V OH

R ~ ^C 6 ^H 5

R = C ^ -C ^ CH ^ OH R ₂ = -CH ₂ -CH ₂ -CH 3 ^CH

orange golden yellow

SOjNa

English Translation:

golden yellow

. Example number

Diazokomponenta

^Ko Pulečný component

NH ₂ NH ₂ R 2

NH ₂

NH ₂ h =. - --CH ₂ -CH _j - ^ ^'N ° 3 N 2 ^{= R} 4 ^{_С Н} 9 <п) ^R 2 = C ₄ H ₉ (n).

»1 = -ch ₂ -ch ₂ —θ ^ ⁵ ° ^{3Νβ R} 2 = -C ₄ H ₉ (n)

100 ALIGN!

101

102

Color shade of golden yellow golden yellow orange scarlet yellow yellow

-nh ₂

nh ₂

^r ₂ = -СН _г -СН ₂ ~ 0Н ^R 1 =, -CH ₂ -CH ₂ -CH, -O-SO, K ^R 2 = -C ₄ H ₉ (n) ³ yellow ^R 1, 2 = " ^CH 2 ^-CH 2" ^CH 2 ^-O- SO ³ K Yellow ^{R | =} - £ y ^with ° ^3N * golden yellow ^R 2 = - ° ₄ ^H 9 ⁽ⁿ > orange R = ^H 2 - 2 ° ~ ^{Н _с} Н ^{г -СН г -ОСОСН} ₃ golden yellow _{R] =} _ £ y ° ^with 3N. . golden yellow

^R2 = C ₄ H ₉ (n)

WHOSE

103

Example number

Diazokomponenta

104

105

cooch ₃ —nh ₂

106, COOCH ₃ / γ-NH 3

107

Í08

109

110

Co-ordination knmmpnoslta Color shade. z- ^ SO ₃ Na ⁼ — —CHj — С у yellow z — x ^ SO ₃ Na

R = —CH3 —CH3 — УТ yellow

R ₂ = C ₄ H ₉ (a)

R1 = -CgH4 yellow · ^R2 '—CH2 ~ ^ CH2 ~ / ~ y ° ³ *

R, 2 = -CH 2 -CH 2 -CH ₂ -O-SO ₃ Na yellow

1

cooch ₃ —HH ₂

112

113

114

Cl

R 1 = -R 11 = -C 1 -C 4 -OH

R 1 = - £ y ^with 3 ^N '• R 2 = -C 4 H 8 (n)

R 1 = C ₂ H ₅ ^R ₂ ^{= 4} y SO ^{3 Na}

R = _ny ^N ° 3 ^with R2 = _-CH2-CH2-CH2 -0C0CH ₃

R,, ₂ = -CH ₂ -CH ₂ -OH orange golden yellow golden yellow golden yellow golden yellow

115

R ₂ = - (H 1 -C 4 -Ol golden yellow ^{R @} 1 = - ^{C2 H5} golden yellow ^R 1 = - ^C 2 ^H ₅ golden yellow R ₂ = -C 1 -C 4 -OC 4 -C 4 -OH

AND

Coupling component Color shade

Example number

116

117

118

119

120

121

122

123

124

125

126

127

128

Diazokom leastenta

^R 1 ^{= "G} 4 ^H 9 ^{(n) = R} 2 - ^GH 2-C ^H 2 ^'O - ^CH 2 ^CH 2" ^OH _χ Η ° ^R 1 = -CH ₂ -CH = CH ₃ R ₂ = -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OH

^R 2 ⁼ -CH ₂ -CH ₂ -0H

R ₂ -CH ₂ -CH ₂ -CH ₂ -0H

r ₂ = -ch ₂ -ch ₂ -o-ch ₂ -ch ₂ -oh

,. 0 ' ^{! O1N} ·

golden yellow golden yellow orange orange orange yellow golden _{Rj 0} = H yellow i, d.

\ - ~ \ J orange OCH3 R ₂ = -CH ₂ -CH ₂ -CH ₂ -OH r = -с ₂ -с ₂ - / - ² scarlet R _{1 2} = -CH ₂ —-CH ₂ —O-ar scarlet ' ^{X ==? X} SO3Na ^CH 3 V * · R = CH ₂ -CH ₂ - ^^ ^_ SOjNa ®2 ° C ^H 2 ^CH 2 C ^H 3 ^_0_ scarlet.

Coupling component

Color shade

Scarlet

Example Diazocomponent number

SO ₃ Na

^r ₂ = ^-C 4 ^H 9 ⁽ⁿ >

, _R]

r ₂ - -CH ₂ -CH ₂ -CH ₂ -O-CH ₃

R ₂ = -CH ₂ -CH ₂ -CH ₉ --OCOCH ₃

Rj = -C ₂ H ₅ yellowish red yellowish red yellowish red scarlet

R 1 = -CH ₃ -CH ₂

SO ₃ K

Yellowish red

^R1 = ^R2

yellowish red

R ₂ = -CH ₂ -CH ₂ -CH ₂ -O-SO ₃ K ^R 1,2 ⁼ —CH ₂ —CH ₃

SO ₃ For golden yellow

R, = _ ^ 0- ^S ° 3 ^N · ^R 2 ⁼ 1 -C ₄ ^H 9 ' ⁿ ) golden yellow orange

golden yellow

138

Diazokomponenta

The coupling component

COOC ₂ H ₅ ^R 1 = ^R -1.2

• ^R2 =

COOC ₉

CoOC ₂ H ₅ ^R 1 = —C ₄ H ₉ (t)

—C ₄ H _g (t)

SOjNa —CH, —CH,

SO ₃ Na ^R 2 =

C ₄ H _g

XOOCH3

COOC ₃ H ₇

NH ₂ ^R 1 = ^{R 8} . =

- ^C 2 H ₅ .

—CH ₂ —CH ₂ -O-CH ₂ -CH ₂ -OH

SO ₃ H

^k , 2 ^-CH , ^{CH3 /} _SO2N .

SQ ₃ Na

R 1 = —C 2 H ₅ ^R 2 = —O>

^ = ^< 'SO3Na

OjN-Q-NH

R 1 = -C ₂ H ₅ R ₂ = - ² So3n

R = - CH ₂ --CH ₂

$ O ₃ Na

Rg = - —C ₄ H ₉ (t)

O

^R 1, 2 = —ch ₂ —ch ₂

SO ₃ Na

Color orange orange yellowish yellow orange yellowish yellow yellow scarlet yellow pale yellow.

O

Color shade example

Number

Biesokomponenta

Coupling component golden yellow

150

152

C ₄ H ₉ W ^NHCO \

153 ^SO3M * yellow, "ЛО ₃ Н» yellow

--CH ₂ -CH ₂ - (J?

₁₅₁ (г.К о'-С ^ »^ ² c ₂ H ₅

C _tt H @ ₉ NHS-O ^'HH2

O

CH, CO -NH rh ⁵ ° ^3Na -СН ₃ -; ^СН 2 ~ \ _S J Green Yellow Yellow // - ^ ^s ° ^3No gh ₂ -ch ₂ - \ J>

// - in ^s ° ^3Ne сн ₂ -сн _а - lrv ^s ° ^3He ch ₂ - CHr- ^ JT

Scarlet Scarlet Brownish Red Yellow

161 i

Diazokomponenta

KoouueČní. komeonenta,

Color shade yellow

Example 0 number

162

R = c ₂ h ₅ ^R 2 = -CHg-CHg-OC 1 -CHg-OH a

. . / ° ^зК

KO ₃ $ —ζ ~ \ - Ν = Ν-ΖΛ— N Η 2

R = C ^ -C ^ -CgH й ₂ = -C-CH₂-OH

Rough blue Rough = ^R 2 = -C 1 -CH-C 1 -C 1)

NH ₃

Rj = H shabby

R | = c ₂ h ₅

R | = C ^ HgCn)

R = c ₄ H ₉ (i)

R 1 = -CHg-CHg-CHg-OH

R 1 '= -CH ₂ -CH ₂ -CH ₂ -O-CH ₃

N = N

R1 = —CH2 — CH ₃ - yellowish ěn г г vr vr vr vr vr vr vr vr

.. red-fronted

Diazocomponent Example

Number

Coupling component

Color shade

173

174

175

176

177

178

179

Rj = red ^R1 = ^C 6 ^H 13 ⁽ⁿ⁾

R = C ₈ H _{| 7} (i) red red

^{R @} 1 = - ^{C2 H5} scarlet R = -C _a H-0-CH 2 and 4 3 scarlet ^R 1 = ^C 2 ^H 5 ruby

yellow

^H 2 ^C CONH, γ 4 ^NH ₄ ^c 2 ^H ₄ o-s ₃ H nhr ₂

180 Q-nh NH, R ₂ = -C ₂ H ₅ red 181 O-*- Νί-θ-ΝΗ R ₂ = -0 ^ (1 ») red 182 O-x- N · —NH ₂ ^{R2 =} - ^c ₄ V ⁿ⁾ red 183 O- ^N - = N - NH _a ^R 2 ^{! =} ~ O bluish red 184 O- = N-NH ₂ ΖΛ- ^R2 = ^ O- ^CH3 bluish

and

185 red / COOCH ₃ {V ™ ²

186 golden yellow

Example number

187

188

189

190

191

192

193

194

195

196

197

198

199

Dlazocomponent d'^ OOCHj

NH ₃ , COOH ₃ , N-NH 3, COOCH

Q-HH, '

COOCH

nh ₂ yCOOCH ₃ θ-ΝΗ, ^ ^OCH 3 NH 3.

By copolymerization 'Color shade r ₂ = -c ₂ H ₅

R ₂ = -¾¾ r ₂ = -c ₄ H ₉

H ₂ =

B ₂ = -c ₂ h ₅ r ₂ = -c ₄ H ₉ ^B 2 = ~ O r ₂ = -c ₂ h ₅

R ₂ = -C (Cn) r ₂ = -c ₄ H ₉ (n)

NH - C ₂ H ₄ O-SO 3 Na

R = -C ₂ H ₅

R, = -C (lower)

R, = -C ₄ H _g (n) golden yellow golden yellow golden yellow golden yellow golden yellow golden yellow.

orange reddish yellow reddish yellow

Reddish yellow yellow yellow yellow

Dlazokomponenta

Coupling component

Example number

200

201

202

203

204

205

206

207

208

209

210

1

212

213

COOCH

nh ₂

^R 1 ^{= C} 2 ^H 5

_T R = C ₃ H ₇ (n)

^{R @} 1 = - ^{C2 H5}

_RT = C ₄ H ₉ (n)

Color yellow yellow

Yellow golden yellow golden yellow

X golden yellow reddish yellow reddish yellow reddish yellow reddish yellow reddish Yellow

Marlatot scarlet bluish red

Coupling component

AND.

and

215

216

219

Example Diazocomponent number

217

218

NH ₃

* 1

H,

Blue-red tint

H ₃ C conh ₂ ^R 1 = - ° 2 ^H 5

R ₁ = -C (Cn)

R ₁ = -C ₄ H ₉ (n)

R 1 = -CH ₂ -CH ₂ -O-CH ₃

CH,

* 1 \ - ^C 2 «5

R ₁ = -C ₄ H ₉ (n) ^R 1 = ^-C 8 ^H 17 ⁽ⁱ⁾

Rj = -C ₄ H ₉ (n) red red red red bluish red bluish red bluish

Red bluish red bluish red bluish red bluish red bluish red bluish red

Example Diazocomponent number.

Coupling component

Color shade bluish red bluish red

bluish red violet ^R t, 2 ⁼ -CH ₂ -CH ₂ -CH ₂ -O-CH ₃

R _g = -C ₅ H

R ₂ = -CH ₂ -CH ₂ -O-CH ₃ -; -cy ^{, 0J} · ^R 2 ⁼ -CH ₂ -CH ₂ -CH ₂ -O-CH ₃

r ₂ = ^ c ₂ H ₅ violet violet orange orange orange

SO2Na orange • ^{R2 =} ' ^C 2 ^H 5

In dye parts of formula · · ''

Wč,

Example 1 h d 23β

Cl

CN HjC. Ν_N_NN = ^ M _- Q-HH-CH3-CH _and -40

NH-CH 1 -CH 2 -O-CH 3 with vigorous stirring. At room temperature, add in portions to 160 parts 20% olea, mix for 3 to 5 hours at 30 to 40 ° C and after completion of sulfornce, pour approximately 1,000 parts ice, 500 parts water into the mixture with vigorous stirring and 300 parts of 50% sodium hydroxide. After addition of 50 parts of sodium chloride, the resulting mixture was stirred at about 10 ° C for 2 hours.

The mixture was filtered and washed with brine. After drying, about 50 parts of an orange-red powder product is obtained, which in water, dissolves into a golden yellow solution and dyes the polycaprolactam fabrics in golden yellow shades with very good fastnesses. ,

Example 239. ·

19.7 parts of 4-aminobenzene are stirred with about 30 parts of 30% hydrochloric acid overnight, then about 150 parts of water are added, the mixture is cooled to 10 ° C, 32.5 parts by volume of 23% are added. sodium nitrite solution and the resulting mixture was stirred at 10-15 ° C for about 3 hours. Any non-diazotized 4-aminoazobenzene, if any, is filtered off, or any excess nitrous acid present is decomposed in the usual manner and · the diazonium salt solution is added to the solution of 56 parts of the coupling component of the formula

SO3M ·

SO3N * in approx. 300 parts water and 10 parts 30% hydrochloric acid cooled to 5 · ° C. Add trlethylamine to the mixture until a pH of about 3 to about 4 is achieved.

©

2HNÍC ₂ H _{s) 3} filtered and dried. A red powder product is obtained which dyes the polycapolymers in scarlet red from shadows with excellent fastnesses. .

Analogous methods can be used to produce dyes summarized in the following:

Example 'Dye number.

240

Color shade on polycaprolactam and red-brown wool

241

242

COOCHj

SO ₃ For golden yellow yellow-orange

243

NH-CM ₂ -CHi-O-SOaNa

red

244

_{NH-CH2 -CH2 -CH2 -O-SO3} to orange

245 \

red

SO3NB

orange

246

202534. . 4 48 _ • · · · -; - ·. Example number Dye Polycaprolactm shade 'a H ₃ C CN wave 47. y —- f V— ~ ~ H C C ₄ H ₉ (n) —NjW / у-MH-CH-CH ^ ~ ^Y ° ^3Na Aarvan ♦ . ^оЛЛ ^ L- ^{= N} CH3. ' ^_CH 2 ^_ ? ^H ~ CX h ₃ ^SO ' ^N ·

AND

0 Й 3 а С со м Р Р т 0 гЧ о О Ь & Р 0 ř> Coll Coll Sat Coll Coll Coll ф >> Р Р Р Р Р Р Р й гЧ 3 3 3 3 3 3 3 0 О гЧ гЧ гЧ гЧ гЧ гЧ гЧ CQ Р. * 3 > ы *) > « Ж «М ж

£ £ & '>> Coll Coll ф ф ф ф Р -Р Р i> > > > 3 3 3 (Ч гЧ гЧ гЧ ф ф ф ф > ы ж ш Ю ‘ ю ю

.ututly red

W л 33 X z-s о о X см О о о о см см о к см см m m X * X <п X к . .->. о о z — S no о CM см см см см см см No. X X X X X no ω о сз о О о о

χ см

о X X X X X X X см о о о о о о о X см со ом ом 00 оп го о X X X z-ч .—. ом о CXJ о О см см см X ом X см ом X X X о X О X X о о о о о ω

X CM

X о

СП

CM ж о

χ ·

X X X X X X X X Ό 0 гЧ О л: н мч со СО СП о см со м · ш Ич S4 м · US US US US 1Г \ US ГЧ ю см см <4 см см см . см см

40 00 σ> о _ N US US US US 40 vo <o см ом CM CM CM CM CM

Ъ φ <y ω t>>>

к к b

Example Y Y. R. R Color to polycaprolactam number

Ю XJ Ю χυ KU > ф > > > CD and <0 P -P P 3 ï rP rd H > N M4

t> к

0)> к

0)

&

Ю *

Ф> k

and к ж Ж ж ж ж о ж O O O о о о о см о rn CM CM m (М СП Ή ж см z-x ж ж <^ ч ж Z — к ' ϋ ж CM O O см о  см см см о Ж CM CM Ж см ж ж ж см O ж ж О ж no о no ж O no о ч_х * “* о

ж ж ж ж о о о о m см гп гп ж см no см см ж см ж ж о ж о о ж ж ж о ж ж

а ² <п си m сп гп СП о ж Ж ж · Ж Ж Ж ж ж ω о о о о о Q

ίΓ Ж со со • -к гп сп сп 'сп СП СП О о Ж Ж Ж Ж ж Ж СО ω ж о О О О О no в

cnin ко КОKD

CM CMCM ко КО CM> KD

CM

00 ОК о КО КО с- г- см см см см

Φ Φ Φ Φ > > t> - > h . h Φ Φ Φ Φ Ю Ю TO) Ю

ф>

ф ю £

ф> ь ф ю

ф> г.

ф ю

· &

ф>

ф X)

no c> я O íM O CM Я cn к O X—. in Q OJ OJ я CM and Я CM я O O O O

я я я я о о о о сП см OJ сп я я Z-ч 1ГЛ OJ Q ϋ OJ Я X СМ см я см О я я о ω о о - '

СП

) я 1Л Ch о о см я и см я о X я я см см см • е я о о О о

я я я о о о СП см ГЛ Z-4. я z ^. ш см 1Л о см я я я см я см о см я · о о - ' о о

н СП . СП сп СП я Я  Я Я о о о о Jm гл СП сп СП я Я Я Я о о о о

ГЛ сп СП СП СП Я Я Я Я Я no о О О no <* сп Я СП СП сп СП О Я Я Я Я о о О О no

Ή

О г — I и »Н Ю

СМ гсм сп г * см

-мίου

1ГЧ осм

LD С— е-ίου ου

σ \ о í— t— 00

OJ CM

Example Z -Y Y '. . R R Color

Number * of polycaprolactam

£ ω

>

φ KJ w

> CD

P

H * 5

· & m. t> t <· φ Ю > φ > Φ 0 Φ P > 0 H Φ Φ Ю Ю

ЕС я ж O O O m m CM of — 4 Г-s Я OJ CM O se w CM ω O я O

ЕС OJ

Я se O O O OJ CM OJ я Я se O O O CM CM CM Я К я no O O

Я я Я я О о о о CM см см см я я Я я о о no о CM СМ см см я я я я о ω о о

Example Z Y Y R R Color shade to polycaprolactam number

q

O)>

ω

XJ

ÍC OJ ÍC OJ ж OJ X OJ к OJ ж OJ ж 0 M O O O O O O о O OJ OJ OJ OJ OJ OJ о OJ ÍC ÍC ÍC tc ж ж ж Ж O ω. O ω O O о O OJ ’ OJ OJ OJ OJ Oj 0 OJ ÍC ÍC К ж ж Ж ж ÍC O ω O ω O ω ω O • - ''with '- ,

X O

OJ OJ го ГО Ж Ж О о 'ъ-' ж ж о · - о о- о ГТ со OJ OJ ж ж no о го со Ж Ж ® - X о - О и " о

—OJ coσ>

OJOJ roLO coco oj OJOJ vo o-co co coco

OJ OJOJ

299 NaO ₃ S — Z VN == M— 0Η _β CH ₃ CH (CH ₂ ) ₃ C (CH ₃ ) ₂ (CH ₂ CH ₂ 0) ₂ H red

Example Z Y Y * R R The color shade of the polycyclic tank number

SO ₃ Na

ж o X X X X X X CXJ O O O O O O X CXJ CXJ CXJ CXJ no X X X X · CM. ϋ O O O CXJ CXJ X CXJ CM CM CXJ X X ϋ X X X X O O O O O no

c \ | X z-4 O m • ’Φ X Z — 4, O . CM X X o ---. O O X X O O O CXI rn CXJ X X O CM irx ď \ CXJ no X X X X CXJ X X O. XD CXJ 4.. . O X o - O ϋ CJ X O

rd rd rd rd • Q O O O

m X O m X O rd O rd O rd ’Q rd O rd. ϋ

.55

Add Z Y and R R Color to number ’. polycaprolactam '

Example number

Dye

Color shade

SO ₃ Reddish-blue

blue

318

SO3No bluish red

Scarlet

Red scarlet nh-ch ₂ —ch ₂ —OH c COH ₂

-4-NH-CH ₂ -CH ₂ - NH-CH ₂ -CH ₂ --43

NH-CH ₂ -CH ₂ -O-SO ₃ Na

šlutooranŽový

321

Example number

Dye

Color shade

322 z

red

323

red

325

326

327

328

329

£ ₂ H ₄ OH yellow red orange yellow yellow red ch ₃

Example number

Dye

Color shade зз:

orange scarlet

331

CONH? SO3Na

NaOjS

bluish red

332 ·

yellow

333

Yellow

Claims (2)

A process for the production of water-soluble azo dyes of the 2,6-diaminopyridine series which, in the form of free acids, correspond to the general formula I in which: D stands for. the rest of the diazocomponent E represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a phenyl group or a methylphenyl group; Z is cyano or carboxamido, R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be interrupted by oxygen atoms and substituted by a hydroxyl group, an acyloxy group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms. carbon atoms, cyano, cyclohexyloxy, phenylalkoxy having 1 to 2 carbon atoms in alkoxy. phenoxy or tolyloxy, optionally hydroxy, chloro, hydroxyethyl, chloroethyl or C 1 -C 4 alkyl substituted C 5 -C 8 cycloalkyl or C 7 -C 15 polycycloalkyl, C 7 aralkyl up to 15 carbon atoms, optionally with hydroxysulfonyl, chloro, hydroxy, methoxy, ethoxy, methyl, ethyl, hydroxyethyl or hydroxyethoxy substituted phenyl, allyl, C 2 -C 6 pyrrolidonylalkyl or 2-carboxyalkyl up to 6 carbon atoms in the alkyl moiety, or two R radicals, together with the nitrogen atom, may form a pyrrolidine, piperidine, hexamethyleneimine, morpholine or N-methylpiperazin ring and have a value of 1, 2 or 3, characterized in that .učeniny a of the mines of the formula dnh ₂ are reacted with the coupling components of the formula in which the formulas D, E, R and Z are as defined above, wherein the group or groups SO 2 H may be present both in residue D and in residue R. 2. The process according to item 1, for producing azo dyes which, in the free acid form, correspond to the general formula Ia (sat ₃ H) _n (Ia) in which: D, Z and n have the meanings given in 1 a R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be interrupted by oxygen atoms and substituted by a hydroxyl group, an acyloxy group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, cyano, cyclohexyloxy, phenylalkoxy up to 2 carbon atoms in the alkoxy moiety, a phenoxy group or a tolyloxy group, optionally a hydroxyl group, a chlorine, a hydroxyethyl group, a chloroethyl group or a C 1 -C 4 alkyl group substituted by a C 5 -C 8 cycloalkyl group or a C 7 -C 15 polycycloalkyl group C 7 -C 15 aralkyl, optionally hydroxy, sulfonyl, chloro, hydroxy, methoxy, ethoxy, methyl, ethyl, hydroxyethyl or hydroxyethoxy substituted phenyl, allyl, pyrrolidonylalkyl; (C 2 -C 6) -alkyl or C 2 -C 6 -alkyl-carboxyalkyl, characterized in that the diazoline compounds of the formula 202534 60 DNH 2 is reacted with the coupling components of the general formula in which the formulas D, Z and R are as defined above, wherein the group or. SO 2 groups can be present in both D and ^{R 4} ;