DE1901711B - Process for the production of azo compounds - Google Patents

Description

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zolyhAcyloxybenzthiazolyl-, furyl-, / Ι-, imidazolyl or benzimidazolylibe «also substituted, but free from groups, alkyl or alkenyls 10 carbon atoms, one titled, but of a protonization-free phenyl radical or a radical

β «]
se!
Kc
tet,
gni
Re =
dui

! atom or one of the meanings in an optionally substituted sst, with ί to 8 carbon atoms, ι A! k) l or phenyl radical, an on.yl or benzoyl radical or R ₃ with the nitrogen cyclic ring system bonded to it with bis men .

the diazo components are phenyl, naphthol, thiazolyl, idiazolyl, pyrazolyl, imidazoyl; e. Aliphatic or alkyl unsaturated and preferably 1 to 8, in particular 1, 2, 3 or n are to be understood,
«Te are those of the formulas

couples, what R ₁ , R ₂ , R ^ and R _{4 have} the meanings given.

Preferred ones made according to the invention; Compounds are those in which R _{3 is} an alkyl radical with 1 to 6 carbon atoms which is optionally substituted by chlorine or bromine atoms, cyano or alkoxy groups, and one optionally by chlorine or bromine atoms. Hydroxy, alkyl, alkoxy, alky! Amino, dialkylamino, nitro, cyano, acyl, acyloxy or acylamine liposubstituted phenyl or benzyl radical, a naphthyl, alkoxynaphihyi, thienyl, methytthionyl, benzthiazolyl -, Methoxybenzthiazo- - odcfR - V -,

Any substituted and / or free hydrocarbon radical, pre-I or phenyl radical, X a group -, - Ο —CO —or — SOj-, om or R. Y a group of 0 - or - NR "—SO ₂ - and 10m or R.
of character can Sub *

B. halogen atoms, in particular

¹ IUuN, vlJlflr- <yJer bromine atoms, nitro, cyano, rhodane. Hydroxyl, alkyl, alkoxy, phenyl, pheeyloxy, alky '. :: nino, dialkylamino, phenylamino. Acyl, acyiov / · or acylamino lip.

The aciiatL ':> cn alkyl, alkenyl and alkoxy groups generally contain 1 to 8, in particular 1, 2, 3 or 4 carbon atoms, like the aforementioned aliphatic radicals as substituents ζ. Β. Halo'cnatomc, preferably chlorine * or bromine atoms, cyano, rhodan, hydroxyl, alkoxy, phenyl, phcnyloxy. Carry acyl or acyloxy groups. Alkyl radicals are also understood as meaning cycloalkyl radicals, in particular cyclohexyl radicals.

Groups that can be protonated are those containing nitrogen To understand residues that in acidic medium, especially mineral acidic medium, a proton attach. The dyes according to the invention are practically insoluble in water.

I 901711

Preferred dyes correspond to the formula

Bi

OH B,

in which D a optionally by chlorine * or Bromine, hydroxyl, cyano, rhodan, nitro, Methyl, ethyl ·. Trifluoromethyl. Meihoxy ·. Ethoxy, Formyl, acetyl, propionyl, benzoyl, methylbenzoyl, Mcthoxycarbonyl-, Älhoxycarbon / I ·, Älhoxycarbonyloxy ·. Benzyloxycarbonyloxy-. Acetoxy, propionyloxy, Benzoyloxy, methoxyethoxycarbonyl, acetylamino, propionylamino, benzoylamino. Methoxycarbonylumino-.Athoxycarbonylamino-.Methylsulfonyl-, Ethylsulfpnyl-, propylsulfonyl-. Butylsulfonyl, Chloromethylsulfonyl, aminosulfonyl, methylaminosulfonyl, Dimethylaminosulfonjl-, Di- (hydroxyethyl) - aminosulfonyl-. Cyclohexylarninosulfonyl ·. Phcnylaminosulfonyl-, Chlorophenylaminosulfonyl-, Methoxyphcnylaminosulfonyl-, Bcnzylaminosulfonyl-, N-piperidylsulfonyl-, N-morpholinosulfonyl-, Methylsulfonyloxy ·. Athiylsulfonyloxy-, Äthoxyäthylsulfonyloxy-. Propylsulfonyloxy, hexylsulfonyloxy, cyclohexylsulfonyloxy, chloromethylsulfonyloxy, cyanoethylsulfonyloxy, Phenylsulfonyloxy-, chlorophenylsulfonyloxy-, Aminosulfonyloxy-, N-morpholinosulfonyloxy-, Methoxyphynylsulfonyloxy-. Ethyleniminosulfonyloxy-, Mcthylaminosulfonyloxy-, Älhylaminosuironyloxy-, Propylaminosulfony.oxy-, Butylaminosulfonyioxy-, Dimethylaminosulfonyloxy-, Oiäthylaminosul / onyloxy-. Dtpropylaminosulfonyloxy-,

■ 5 Dibutylaniinosulfonyloxy-, Phcnylarninosulfonyloxy-. 14 Phenyl - N- meihylaminosuironyloxy-, N - PhenyI-N-ethylaminosulfonyloxy-, Mtfthoxyphenylaminosulfonyloxy-, Phetiylambo-, nitrophenylamino-. Dinitrophenylamüio-. Phenyl-, Acctylaminophcnyl-, Phc-

To nylaminosulfonylphenyl, Phcnylazo- or nitrophenylazo groups substituted Phcnylrest, a naphthyl radical optionally substituted by methoxy, alhoxy, phenylazo or dimethylaminosulfonyl, an optionally substituted by chlorine · or

»S bromine atoms, nitro, cyano, methyl, phenyl, methylsulfonyl or Ethylsulfonylgruppc substituted Thtazolylrest, one optionally by chlorine or Bromine atoms, cyano, N'itnx methyl, ethyl. Methoxy, Athoxy-, Methylsulfonyk Äthylsulfonyl-. Cyanithyl

y> sulfonyl, aminosulfonyl or methylaminosylphonyl groups substituted benzothiazolyl groups. a Pyrazolylrcsi optionally substituted by cyano, methyl or phenyl groups. a thiadiazolyl radical optionally substituted by a methyl group, an imidazolyl radical optionally substituted by nitro or methyl groups, a thienyl radical optionally substituted by nitro or acetyl groups, or a radical of the formula

B, an alkyl radical with 1 to 4 carbon atoms which is optionally substituted by chlorine or bromine atoms, hydroxyl, cyano, methoxy or ethoxy groups, one optionally by chlorine or bromine atoms; J ₀ methyl, methoxy, nitro, methoxycarbonyl, ethoxycarbonyl. Melhylaminosulfonyl-, dimethylaminosulfonyl-. Cyan- ^ xIer acetylamino groups substituted phenyl, a naphthyl, methoxynaphthyl, ethoxynaphthyl, thienyl, methylthicnyl, furyl, j ₅ thiazolyl, pyridyl, imidazolyl or benzimidazolyl radical, B ₂ a cyano, propionyletyl ·, Methylsulfonyl, ethylsulfonyl, benzoyl. Phenylsulfonyl, nicotinoyl, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl or di- ^ ₀ äthylaminocarbonylgruppe and B _{3 is} an alkyl radical with 1.13 or 4 carbon atoms, optionally by chlorine or bromine atoms, hydroxyl, cyano, methoxy -, Alhoxy-, Methoxyäthoxy-, Cyanälhoxy-, Phenoxyäthoxy-, Acetyl-, Propionyl-, Benzoyl ·. Formyloxy, atetoxy, propionyloxy, methoxypropionyloxy, acryloxy, benzoyloxy *. Methoxycarbonyl, ethoxycarbonyl, ethoxyethoxycarbonyl, cyanomethoxycarbonyl, phenoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy, phenoxycarbonyloxy, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, methylaminocarbonyloxy, pharbonyloxy, methylaminocarbonyloxy, pharbonyloxy, methylaminocarbonyloxy,. Methoxycarbonylethoxy, 5-chlorofuryl (2K methylsulfonyloxy. Ätbylsulfonyloxy-, Phenyisulfonybxy-, vinylsulfonyloxy, phenoxysulfonyl, penthioethylsulfonyl or vinylsuliönyl, · ethylaminoyl, methylaminoyl, methylaminoyl, trimethyl, ethylaminoyl, methylaminoyl, trimethylamino-, methylsulfonyloxy-, phenyisulfonyloxy-, methylamino-, dimethylaminoyl. Hydroxyethylamino, di (/ <- cyanathyl) amino, di (acetoxyethyl) amino, phenylamino, ethoxyethylamino, formylamino, acetylamino, propionylamino, benzoylamino, N-piperazyl, N-pipcridyl - or N-morpholinyl radical or a radical of the formula

■ so,

means.

The compounds of formula (III) are made by diazotizing an amine of formula

R ₁ -NH ₂

and coupling the resulting diazomum compound with a compound of the formula

αϊ)

OH R ₄

manufactured. Analogously to this, Iic compounds of the formula (IV) by coupling a diazotized Amine of the formula

D-NH, (V)

with a compound of the formula

(VI)

OH B ₁

., compiled The coupling generally takes place in It is to be assumed that the compounds of the form

'acidic, optionally buffered medium below 35 mel (III) or (IV) in a tautomercn state, the

Cooling instead of As a bulking agent comes from the formulas in particular Sodium acetate in consideration I.

R, R ₃
OH R ₄

R ₃ R ₂

N - <^ ~~ V- OH
OR ₄

marked is available.

The coupling components [of formula (IV) or (VI)] are prepared in analogy to the method of J. Guareschi, Atti Accad, Rd Scienze di Torino [1895/1896], special edition (cf. also Bcr. O. Dt. chsm. Ges, 29 [1896], & 655, Chem. Zentr. [1896) J.602: [18%], 11.46, and ümaprasynna B as and Journ. Indian Chem. SoC ₇ VoLVIII [193!]. P. 319 to 328), by condensation of appropriately substituted acetic acid amides or acetic acid hydrazides with appropriately substituted / t-octocarboxylic acid esters.

It is particularly advantageous to use the new To transfer dyes to ir. Dye preparations prior to their use. The processing to color preparations takes place in well known manner, e.g. B- through Milling in the presence of dispersants and / or fillers. With the possibly in a vacuum or Preparations dried by spraying can be used, after adding more or less water. in so-called long or short liquor colors, padding or printing.

The hues. draw from an aqueous suspension onto fibers or threads and from them

ss manufactured textile materials from fully or semi-synthetic, hydrophobic, high-molecular organic Fabrics on. They are particularly suitable for dyeing, padding or printing textile material from linear, aromatic Pclyestem, from cellulose *

te 2Vj-UCeUl, cellulose triacetate and synthetic polyamides. Polyolefins and polyvinyl compounds can also be colored with them.

One dyes or prints according to known methods, ζ. B. that in French patent 1,445,371 described procedure. The colorations of yellow to red nuances obtained have very good general properties, in particular they are excellent thermoftxicr, sublimated, pleated, ozone, frictional and smoke gas

The wetness is also very good. z. B. the Water. Seawater, sweat. Alkali and washing ci'lnlicii Also to be emphasized are the overdyeing cchtheii. Resistance to corrosion. the Lichicchiheit and the good sense of humor. The dyes are constant against the effects of the various Permanent pressing process. Another advantage is the favorable hiding power of streaky Padding material. The dyes can also be used to dye textured polyester linden.

Structurally similar dyes are from the French Patent specification 767 690 and the Belgian patent specification 685467 known. The next comparison Available, known dyes are according to the invention Dyes, however, in terms of their fastness to sublimation b / v. inferior in the pH siahililal.

The parts mentioned in the following examples are parts by weight and; the percentages percentages by weight. The temperatures are given in degrees Celsius.

Example I.

17.3 parts of 2 - chloro - 4 - nitro - aniline are mixed with 1 (K) TcUCiI water and 25 parts of 30% hydrochloric acid and cooled to Ό. A solution of 8 parts of sodium nitrite in 20 parts of water is then allowed to drop in the course of 15 minutes and the mixture is stirred for a further 30 minutes. SoJ; <and the excess nitrous acid is destroyed with sulfamic acid. After one of small; Has filtered amounts of solid contamination. a solution of 17.8 parts 1,4-diethyl-3-cyano-6-hydroxypyridone-2 in 2 (X) Te>'cn dimethylformamide is added to the clear di.i / .onium salt solution, which has been cooled to 0 to 5, the reaction mixture being kept at 0 to 5 until the reaction is complete. The deposited dye is then discharged. washed neutral and dried. The orange crystals color synthetic fibers * in yellow tones with excellent fastness properties. ;

Example 2

8 4 parts of 2 - / \ minotriazole-l, 3.4 are dissolved in KK) parts of water and 25 parts of 30% hydrochloric acid and heated to 70. After cooling to about 5, a solution of 8 parts of sodium nitrite in 20 parts of water is left add dropwise over i 5 minutes and stir for a further 30 minutes. The excess nitrous acid is then destroyed with amiaosulfonic acid. After one has thiiliricTi of small amounts of fesler impurity, a solution of 16.4 parts of 1,4-diiriethyl-3-cyano-6-hyrirox> -p \ ridon-2 in KK is added to the clear diuzonium salt solution, which has been cooled to to 5 " Share F.isessjg. The dye precipitates immediately in a crystalline form; it is filtered off, washed neutral and dried. The orange crystals give synthetic fibers real yellow tones. ■■

Example 3

17.3 parts of 2 - chloro - 4 - nitro - aniline are mixed with 100 parts of water and 25 parts of 30% strength. Hydrochloric acid mixed and cooled to 0. A solution of 8 parts of sodium nitrite in 20 parts of water is then allowed to drip for 15 minutes and the mixture is stirred for a further 0 minutes. Then destroyed ι; λ \> the übcrscluiU of nitrous acid with Amidosulfonsäurc. After no amounts of solid impurities have been filtered off. gives the solution, cooled to 0 to 5, of 16.4 parts of 1,4-dimethyl-3-cyano-6-hydroxypyridone-2 in 00 parts of water, which with

S a little acetic acid is adjusted to pH 4.0 to 4.5. This pH value is maintained throughout the coupling by adding sodium hydroxide. After the reaction is over. the dye is filtered off, washed neutral *; H dried. The yellow ones

ίο Crystals color synthetic fibers in yellow tones with excellent fastness properties.

A dye with similar fastness properties is obtained if, instead of 2-chloro-4-nitro-aniline, the Diazo bond from equimotecular sets of

■ 5 sulfanilic acid dimethylamide is used.

Example 4

17.1 parts of 1-amino-benzene-4-methylsulfone become in 150 parts of water and 25 parts of 30% hydrochloric acid solved. The mixture is cooled to C and a solution of 8 parts of sodium nitrite is added dropwise over 60 minutes in 20 parts of water. After stirring for another hour. one destroys the excess of nitrous acid with amidosulfone The clear Diazonium salt solution is now in 30 minutes to an ice-cold, adjusted to pH 4 with acetic acid and 19.3 parts solution buffered with nairiumacciai I-dimethylamino-3-cyano-4-methyl-6-hydroxypyridone-2 in 150 parts of water. The color stolT separates out as a yellow powder. After adding the diazonium solution, stirring is continued 30 minutes and isolate! the product. The yellow dye colors synthetic fibers in clear, yellow

Shades with good fastness properties.

A dye with similar lightnesses is obtained if 1-aninobenzene-4-methylsulfone is used instead of 1-aninobenzene the equimolecular amount of 2-chloro-4-nitro-aniline begins.

Example

13.8 Tcilc2-nitro-aniline w ith 100 parts of water and 25 parts of 30% hydrochloric acid dissolved by stirring. It is then cooled to 0 to 5 'and diazotized the amine with 8 parts of sodium nitrite dissolved in 30 parts of water. Mix for another hour and destroys the excess of nitrous acid with amidosulfite. The diazonium salt solution is filtered from any solid impurities that may be present. The diazonium salt solution is then added in small portions to a solution of 19.3 parts made to 0 to 5 and adjusted to pH 4.5 with glacial acetic acid l-EthylaminoO-cyano ^ -methyl-a-hydroxypyridone ^ in 150 parts of water. Already during the encore

The dye separates from the diazonium salt solution as a yellow powder. During the reaction, the pH is kept at about with the aid of sodium acetate 4.5. After the addition of the diazonium solution, the mixture is stirred for another 45 minutes and the

«O Dye, of the synthetic fibers in clear, greenish-tan Dyes shades with excellent fastness properties.

Example 6

22.6 parts of 3-Dimethy laminosulfcnyloxy-aniline are dissolved in 280 parts of water and 36 parts of 30% strength hydrochloric acid and adjusted to 0 to 5 '. Then one diazoiicrt the mixture with a solution of

009 582/355

8 parts of sodium nitrite in 50 parts of water. To the When the diazotization is complete, the mixture is stirred at 0 ° to 5 ° for a further hour and the excess is destroyed nitrous acid with a little sulfamic acid '*. To the Coupling, 25.5 parts of 1-dimethylatin are suspended - 3 - cyano - 4 - phenyl - 6 - hydroxypyridon - 2 in 2S0 parts of water and adjusts the pH value with acetic acid to 4.5. The diazonium salt solution is then added dropwise to the well-cooled coupling solution in the course of 30 minutes, the pH being adjusted with sodium acetate keeps constant. The mixture is stirred for a further 60 minutes and the precipitated product is filtered off away. The yellow powder dyes synthetic fibers in yellow shades with excellent fastness properties.

Example 7

13.8 parts of 3-nitro-anUin are finely suspended by stirring in 100 parts of water and 35 parts of 30% strength hydrochloric acid. The mixture is cooled to 0 ° to 5 ° and the amine is diazotized with 8 parts of sodium nitrite dissolved in 30 parts of water. After the addition of the nitrite is complete, the mixture is stirred for a further hour and then the excess of nitrous acid is destroyed with sulfamic acid. For coupling, 29.8 parts of finely powdered hy-methoxypropyl) -3-cyano-4-ρ-tr <yl.6-hydroxypyridone-2 are suspended in 300 parts of water and the pH is adjusted to 4.5 with glacial acetic acid . After the temperature of the suspension has been brought to 0 to 5 ^{° C.} the clear, filtered diazonium salt solution is added dropwise for 30 minutes and the mixture is stirred for a further 60 minutes. The pH is kept in the range from 4.0 to 5.0 with sodium acetate. The yellow dye is then isolated, washed and dried. It dyes synthetic fibers in clear, yellow shades with excellent fastness properties.

If, in this example, instead of 29.8 parts of l - (; - Methoxypropyl) -3-cyano-4-p-tolyl-6-hydroxypyridon-2 22.2 parts 1 - (; - Methoxypropyl) -3-cyano-4-methy1-6-hydroxypyridon-2 a yellow dye with similar properties is obtained.

Application examples

A. 7 parts of one of the dyes prepared according to Example 3 are mixed with 4 parts of dirtaphthylmethandisulfonsaurcm Sodium, 4 parts of sodium ci)! Sulfate and 5 parts of anhydrous sodium sulfate in one Ball mill ground to a fine powder for 48 hours.

1 part of the dye paralc obtained in this way is made into a paste with a little water and the suspension is obtained through a sieve of 3 parts of sodium lauryl sulfal in 4000 parts of water ^; ι • ♦ ■ white added. The liquor ratio is J ν · Tan now gives 100 parts of purified PVy ^ tcr '. <· ... material at 40 to 50 "in the bathroom, / '.' . ". ■ .. ^T o.; Pure chlorinated benzene emulsified in water too. heats the bath slowly to 100 ^c and stains 1 to 2 hours at 95 to 100 '. The yellow-colored fibers are washed, soaped, washed again and dried. The level dyeing is excellent light, over-dyeing, washing, water, sea water, perspiration, sublimation, smoke gas, thermosetting, pleating and permanent press-fast.

B. 30 parts of one of the dyes prepared according to Example 7, 40 parts of dinaphthylmeihandisulfonsaurw Sodium. 50 parts of sodium cetyl sulfate and 50 parts of anhydrous sodium sulfate are in a ball mill ground to a fine powder.

To 4 parts of the Färbcpräparaies obtained in 1000 parts of 40 to 50 ^C warm water was added 100 parts of purified Polyestcrfascrmatcrial and slowly heated. It is dyed for about 60 minutes under pressure at I30 ~ and obtained after rinsing. Soaking, rinsing and drying produce a yellow dye with the same fastness properties as the dye of the

ie example A.

C. 20 parts of the dye prepared according to Example 1, 55 parts of sulfite cellulose liquor powder and 800 parts of water are ground in a ball mill until the size of the dye particles is below

is I μ lies.

The colloidal solution obtained is diluted with 25 parts of ethyl diglyco! Monobyl ether and 400 parts of 6% carboxymethyl cellulose mixed. This printing paste is very suitable for door polyester

so crest. The printing is done with the help of two rollers (78% coverage), followed by steaming at 120 "without intermediate drying. Yellow prints are obtained of good fastness properties.

D. 7 parts of one of the dyes obtained according to the information in Example 3 are mixed with 13 parts of sulfite cellulose liquor powder and 100 parts of water ground in a ball mill. The paste obtained is through Spray dried.

4 parts of the dye preparation obtained are made into a paste with a little water and passed through a sieve 4 parts of N - olcyl - N '- hydroxyaryl - N' - (3 '- sulfo-2'-hydroxypropyl) -ethylcinediamine added in dyebath containing 4000 parts of water. 100 parts of polyamide material (nylon 66) are then added at 20 in the bathroom. heats this to 100 "within 30 minutes and colors at 100" for 1 hour yellow color is rinsed and dried. She doesn’t care and has good light, care, washing ·. Water, sea water, perspiration, sublimation, friction and solution milky fastnesses.

E. One aqueous, finely dispersed suspension of 30 parts of one of the dye obtained according to the information in Bcispxl 4. 70 parts of dinaphthytmcttu ■ * «- sulfonic acids) sodium and 3 parts of sodium algae ...«.

Put '«earth with water to 1000 parts and mix well. A polyester fabric is obtained with the Padding liquor padded at 20 ". With air of 60 Dried to 100 'and then treated with hot, dry air for 230 60 seconds.

Then the fabric is rinsed, soaped, rinsed again and dried. A level and genuine yellow coloration is obtained.

Fibers made from synthetic polyamides can be dyed in the same way.

In the following tables there are more, according to the Examples 1 to 7 manufacturable dyes.-Η given. All of these dyes have the fastness properties indicated above and apply to polyester fiber material Yellow to red shades of color.

The dyes in Table I correspond to the formula

OH B ₁

At-
«Piel A ₁ A ₁ A, -OCOOCjH, -NO, COOtH, -NO ₁ -SO ₁ CH H -SOjCH H A, A, B, B ₁ B ₁ 8th H H -OCOC ₁ H, -NO, -NKCOCHj H H H "CH ₁ -CN -CH ₁ CH ₂ COOCH, 9 H H -COCH, H -NHCOQH, H H H -CH, -CN -CH ₁ CH ₁ OH 10 H H H -NHCOCH, H H H -CH, -CN the same Il -Br H -NQ, -SO ₁ N (CHj), H H H -C ₅ H, -CN the same 12th H H H the same H H H -QH, -CN -C ₁ H ₄ CN 13th H -NO, H M. H H -CH ₁ -CN -C ₁ H ₄ CI 14th -NO, H H M. H H -CH, -CN the same 15th -CN H H H -CN -C ₁ H, -COCH ₁ the same 16 H -NO; H H H -CHj -CN -CH ₁ CH (OH) CH, 17th H -NO, -NO, H H -CH ₁ -CN -CH ₁ CH ₁ OCOCK ₁ 18th H -NQ, -NO, H H -CH, -CN -CH ₁ CH ₁ OCOQH, 19th H -NO, H H H -CH ₁ -CN -CH ₁ CH ₁ OCOC ₁ H, 20th H -NO, -NO ₁ H H -CH ₁ -CN -CH ₁ CH ₂ OCOC ₁ H, 2t H H H H -CH, -CN -CHjCH ₁ OCOOC ₁ H ₁ 22nd H H H H -CH ₁ -CN -CH ₁ CH ₂ OCOOQH, 23 -NO, H H H -CH ₁ -CN -CH ₁ CH ₂ COOCH, 24 -Cl H H H CH, -CN -CHjCH ₂ OCOCH-CH, 25th H H H H CH ₁ -CN -CH ₁ CH ₁ COOQH, 26th -σ H H -Cl -CH ₁ -CN -C ₁ H ₁ OH 27 -NQ, H H H -CH, -CN the same 28 -CN H -Cl H -CH, -CN -CH ₁ CH (OH) CH ₁ OCH, 29 -Cl H H H -CH ₁ -CN -Ch ₁ CH ₁ COCH, 30th H H H H -CH ₁ -CN deigl. 31 H H H H -CH, -COCH ₁ -CH ₂ CH ₁ COCH, 32 H H H H -CK ₁ COCH ₁ the same 3> -σ H -α H CH ₁ -CN C ₁ H, .M -Cl H H -Cl -CH ₁ -CN -C ₁ H, YY H -0-SO ₁ -N (CH ₁ ), H H -CH ₁ -CN -QH, 36 H the same H H -CH ₁ -CN -CHjCHjOCOCH, 37 H the same H H -CH ₁ -CN -CH ₁ CH ₁ CN 3 * H the same H H -CH ₁ -CN -CH ₁ CH ₁ O 39 H the same H H -CH ₁ -CN -QH ₆ OCH, 40 H the same H H -CH ₁ -COCH, the same 41 H the same U H -CH ₁ -SO ₁ CH, the same 42 H the same H H CH, SO ₁ C ₁ H, the same

Continuation at
game Αι A, Aj -SOjNHCH, H H ₁ NSO, H HjCOCO- -CH, A ₄ A, B ₁ B, B, -QH ₁ OCH, 4.1 -DCH, H NO, OCHj H H ₅ COCO- -CH ₁ H H -CH, -CN dcsgl. 44 H H -COOCH ₁ QH, (HjC) ₁ NCO- H H ₁ COCO- -CH ₁ H H -CH, -CN the same 45 -CH, H -OH H -CH, H H -CH ₁ -CN dcsgl. 46 H H H H ₁ COCO- -CH, H H -CH, -CN -QH ₄ COQH, .... 47 .... H H -CH, H H -CH, -CN dcsgl. 48 H H -CH, H H -CH, -CN the same. W 4 « H -OSO ₁ CHj H H H -CH, -CN the same JO H H Il H H -CH, -CN -QH ₄ SO ₁ CH-CH, 51 H -NO, H H H -CH, -CN KZL 52 H -NO ₁ H H H -CH, -CN. -QH ₄ OQH ₄ CN 53 H -NO ₁ H H H -CH, -CN -NHCOQH, 54 H -NO ₁ H H H -CH, -CN -NHQH, ^ ^- 55 H -NO ₁ H H H -CH ₁ -CN <»> S 5 « H H H H -CH, -CN -QH ₄ OQH ₄ COOCK, * - 57 H H H H -CH, -CN -C, H, 0- ' _v H ~) "*
I. JS H H H H -CH, -CN Cl -QH ₄ OSO ₁ QH, 59 H H H H -CH, -CN riergl. M) -NO, H H H -QH ₁ -CN dMl 61 -NO ₁ H H H -QH, -CN QH ₄ CONH ₁ 62 -NO ₁ H H H -QH, -CN -QH ₄ COOC ₁ H ₄ OCOCh, 6.1 -NO, H H H -CN -QU ₁ OQH ₄ OQH, _m A4 -NO ₁ H K I? -1..Ki -CN -QH ₄ OQh ₄ OCONHQH, * A! NO, H H ' l ·' -C ₁ H, -CN jctpl AA -NO, H H H -CH, -CN dctfl A7 H -NO ₁ " H H -CH, -CN (', H ₄ Or ₁ II ₄ (KH ₁ AK Cl ti -Cl H -CH, -CN 'C ₁ II ₄ (OO (II) CN A4 Cl M. -Cl H -CH, . -CN -CH ₁ CHOHCH ₁ CN 70 Cl H -Cl H -CH, -CN CH ₁ SOjQH ₄ SQH, 71 Cl H -Cl H -ca, -CN -C ₁ H ₄ (KH, 72 Cl H -Cl H -CH ₁ -CN CjH ₄ SO ₁ OQH, 71 Cl H -Cl H -CH, -CN

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ϊ; ΐ: 3 ϊ

w U O t U U U ϋ Cj

S "£

ι ι ι ι ι: ι ι ι ι ι ι

3 *

5 σ

ΙΙίΙΐι

Il Il

δδδδδ: δδ5δ δ δ δ δ δ δδδδδδδδδ

ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι · ι ι ι ι ι ι ι

ι ι · ι ι: ι ι \ ^ τ

ff

O I ι ι ι I ' >

C-O

XXXXXXXX X X X X X χ XXXXXXXX

0 C χ χ χ χ χ I I

SX SX XXXX

XXX X

X X

XX 0 G
ι ι

8 ί

2 Ζ

δ <5

XXXXXXX Z Z

I I

X X

S £ χ χχχχχχχχχ

ΟΟίχζχ

XX XX

X X

ΧΧΟΧΖ XO Z '. ι ι ι ι

S = = == §53255 5

continuation

, H ₄ OCH ₁

-QH ₄ OH

-CjH ₄ OCONHQH,

-C ₁ H ₄ COOCHjCN

H, QN (CH,) SO, OH ₁ QN-SOjO-H -CHjCHOHCHjCN -QH ₄ OKCH ₁ OQH, -QH ₄ COOCHjCN

IHOQH ₄ I ₁ NSO,

CjH ₄ OCOC ₁ H ₄ OCH ₁

QH ₄ OCOCH-CH ₄

-CONHQH, -LON (CHj),

-QiH.CCOCH,

-QM ₁ OCOQH ₁ -C ₁ H ₄ COOQH,

the same

-QH ₁ OCOQH ₁

de »»].
CH,
-QH ₄ SO ₁ OC ₄ H,

-QH ₄ OQH ₄ OCONHQh,

-OH,

H
-CH,

-σ

-NO,

-OH,
H
H

-NO ₁

-NO, H ₁ NSO ₁ - H H ₁ NSO, - H -OH dtiii. H H H H ₁ CNHSO ₁ - -CN -CH, -Cl H H H H -α H HjCNHSO, - -σ H HjNSO ₁ - H H H H

H
H

H
H.

-NO,
H
H

-NOTE
H

H ₁ CCONH-H ₁ COCH ₄ OCO-

CH ₁ SQr

-COCH,

-NO,

-OH.

H ₁ NSQ, -

-OC ₁ H,

-COOC ₁ H,

-CF, -CF,

-Cl

continuation

H
H

H
H

H
H
H

H
H

NCC ₁ H (NHSO,
H

Cl

H
H

'_ H

-CH ₁
-Cl

Il

H H

H H

H H H

-α

H H H

H H H H

H H Il H It Ii

-CII, Il

C ₁ H, -CH,

-CH, -CH,

-CH, -C ₁ H,

-QH, -C, ll,

-CH,

-QH, -CH, -CH, -CH, -CH ₁

-CH,

-CH, -QH, -QH.

-CH, -CH, -CH, -CU _t -CH,

-CN -SO ₁ CH,

-CN

. -CN

-CN

SO ₁ C ₁ H,

roocii,

-SO ₁ -CH,

-CN

-CN

-CN

-CN -CN -CN

-CN

-CN -CN

-CN -CN -CN -COCH ₁

C ₁ H ₄ OCH ₄ HCH,

CIVUOCH ₄ OCOcH,

CH ₄ C) CONlIr ₄ H, -C ₁ H ₄ OCH ₄ OCOCH,

CH ₄ OSO ₁ CH ₁

-C ₁ HtCONH ₄

-C ₁ H ₄ COCH,

CHjCHOHCH ₁ UCH, '-C ₁ ICSlHCM * CH,

'CH ₁ CHOHCH ₁ CN • -CH ₁ Ot ₁ CH ₁ OH CHiH'ONIICI I,

cn,

example

17 «i7 <* IHO

IKI 1X2

184 tH5 Yeh 18th IHH 1X9 1") 191

192

Ι9Λ

194 195 1% HT IW

194

200 201 302

H ₁ C ₁ SO ₁ O H A ₂ A, CHjOCO- -NO ₁ H ₁ CS-V -NQj CH ₁ SO ₁ - -NO ₁ rorKci / unp A, B, B ₁ B, i «3-C, H- A, CH, H H -CHO -NQ, -NO ₁ A ₄ H CH, -CN -CjH ₀ OH -Cl H H U NCCjH ₄ NHSO ₂ - H -CH, -CN QH ₄ COCH, -CH, H H H CIC ₁ H ₄ NHSO ₁ - H CH, CN -C ₁ H ₄ Ct 11, C ₂ OC ₂ H ₄ NHSO, - H O H N-SO) - H -Cl -Cl -CH, -CN CjH ₄ CN H -NO, (H% Nile-SOj- Il H H CH, -CN -QH ₄ COOCjH, H H C.Hj CH ₁ -NHSO, - H CH, H -CH, -CN -C ₁ H ₄ OCOC ₁ H, H -NO, H <(7 ^ KHSO ₁ - • t
. I * Il -CH ₁ -CN QH ₄ OC ₁ H, -Cl -CN H C * 'V NlCHj) SO ₁ - H H -CH, -CN C, H »OCH, K -CN H Cl - <^ κ ^ NHSO ₁ - H H -CH, -CN n-QH, H -NO, -OSOjCHjCI -Cl It H -CH, -CN -QH, CJ H H NC-CjH ₄ SOjO- H H -CH, -CN n-CH, H -a H H H H -QH, -CN -CH, -Cl HsC ₁ OC ₂ H ₄ SO ₁ O- -OH, H -CH, -COCH, IeH-C ₄ H, CH ₁ SO ₁ O- H H H -QH, -CN -CH, -Cl ^{) S} > CHCH, SOjO-
CHj ^/ -CH, H QH, -CN -CH, <^> SOjO- H H -CH, -CH, -CN -QH ₄ OCH, H H H -QH, -CN -CH, H H H -CH, -CN -C ₁ H, H H H -QH, -COCH, -CjH ₄ OCjH, H H H CH, -CN -QH ₄ CN H H Bc CH, -CN H H H -QH, -COCH, H H H -QH, -CN -QH ₄ CON (CHj) J Il H H -CH, -CN -QH ₄ CO- ^ jT) H H H -CHjCHjOH CONHQH, H

(O O

continuation

1IH «pid

-Ht

SOjCM, SO ₁ C ₁ H,

-Cl -CN -NQ ₁ -COOCH,

-σ

-CN

-, NO,

CH, 0C0-

H H

-NO,

H H H H

H H

H H

H H

H H H

-NO ₁
-NO,
-NO ₁
-Cl

-α

-NQ,
-NQ,
-NO »
-NQ,

-NQ ₁
-NO,

-σ

CH ₁ OCO-CH ₅ CO-

QH ₉ OOC H ₁ CSO, -

H H H H

H H H H H

H H H

H H

H H H H

H H H

-σ

-NO ₁

H H H

OQH,

CN
CON (CHJQH,

-COCH ₁ QH, CO-φ -CO-N (CH,), CONH, '

-SQ ₁ NH, -SO ₁ NHQH,

-SO ₁ N (CH,),

-SO ₁ N (CHiIQH, -QH, -CN -QH, -CN -CH, -COCH, -CH, -COOQH, -CH, -CN -CH,

-QH ₄ SOjCH,

QH ₄ SO ₁ QH,

QH ₄ SO ₁ CH ₁ QH,

QH ₄ OSO ₁ QH,

CH, QH ₄ OH

-QH ₄ CN -CH,

continuation

Bd-
«Piel A ₁ H ₁ NSO, - -Cl A ₁ H ₁ CSQ, - A, CH.CO- -NO, CHjSO ₁ - -NQ ₁ A ₄ A, H B, B, B, -QH, 220 -Ci -CH, H CHjSQ ₁ O- H CH.OOC- -NO ₁ (CHj) ₁ NSO ₁ - -a H H -CN -CH, 221 H -Cl H H -CF, H -OH, H H H -CON (CKA -CH, 222 H H H -CH, -NO, H H H -CN -CH ₁ 223 H -a -a H H H -CN -CH ₁ 224 H H H -CH, H -CN -C ₁ H, 225 H H -NO ₁ H H II -CH, -COOC ₁ H, -QH.OCH, 226 H * H -a H H H -CH, -COOCH ₁ QH ₁ -N (CHj) ₁ 227 mc ^> - co- H -σ -CH ₁ H H -CH, -CN -N (C ₁ Hj) ₁ 228 H Ά H H H -CH, -CN -N (CHjCH ₁ OH), 229 -Cl H H H -CH ₁ -CN -N (CH ₁ CH ₁ CN), 230 -σ H H H -CH, -CN -N (CH ₁ CH ₁ O), 231 H H H H -CH, -COCH, -N (CH ₁ CH ₁ OCOCH,), 232 H H <O ^c ° - H -CH ₁ -CN 233 -Br H H H -CH, -CN -NJ ^ O 234 -NO, H H H -CH, -CN -\H] $ 23 P. H -CH, -CN -NHQri, 2M CHjSO ₁ O- H H H -CH, -CN -N (CIi, rQH, 237 ClC ₁ H ₄ SO ₁ O- H H -a -CH, -CN -CH, 238 K ₁ C ₄ SO ₁ O- H H <T> co- -CH, -CN H ₁ QSQ ₁ O- H I.
CH, -CH, 23 » H -QH, -CN -CH, 240 K -QH, -CN -QH, 241 H -QH, -CN -CH, 242 -CH ₁ -QH, -COCH,

w υ y ο

£ 5 "£ 5

C? Z

XX SXI ^s
> ι ι ι ι 'ι · ι · ij ■ T

af £££ ο * Cr ζ ^

x £ £

UUU

111!

X _n ^ ZZZZZZ Z ZZZ C7X SUUUUUU U UUU

8ϊί

I 1: 1 I I.

zzzz -ζ

III I

ZZ

ZZZZ

ι ι ι ι ι ι ι ι

£ S "£ ££££££ £ £ £ £ ο * ο * ο * υ * Cf υ * CT tf ο * tf cf Cf Cf

ι ι ι ι ι ι ι ι ι ι ιιι

U UUUU U
ι ι ι ι ι ι

SSS

ι ι ι ι ι ι ι ι

SUXII =

X XXSX

XX X X XXXX

XXXXXXXXX X XXX

IXXX

χ xS

χ χ χΰχχχχ

χ χ χ χ χι χ

rf

f fe ί

UUU XSX

O «a XXXXXX ι
C.

£
Cf

i-x-V s

XXXXXX

i ^SI ά

XXX · = »§ · ?. I 55 "χ

U U <4

■ ¹ SS

UXX

ΐϊ

XX.OxS-Xxi X

β δ; μ

if; 3

c
CoS

© χ

uxxc

I ^s ^ - · <"-

° »J» ² H ^

S * = χ

continuation

Bd- A. A, A. A, A, B, B. B. -QH, m H (H ^ QJ ₁ NSO ₁ O- H H H -C ₁ H, -CN CH, m H 0 H N-SO ₁ O- H H
! H -CH, -CN CH, 274 H <H> «>, 0- ... ........ H ._ . H H -CH, -COCH, CH, 27S H ^ NHSO ₁ O- H * H -CH, deigl. CH, 276 H <^> N (CHJSO ₁ O- K H H -CH, do,,, -CH,
-CH,
-CH, 577
27 »
27 » H
H
H
CH, -CH,
H
-CH, (H ₁ C) ₃ N ^ O ₁ O-
dctgl -CH,
K
U XXX -CH,
-CH,
-CH, like
COOQH,
dcigt. -CH ₁
-N (CH ₁ J ₁ 280
2Il H H
^) - N (C ₁ H ₁ JSO ₁ O- -CH,
H -CH,
H H
H -CH,
-CH, dctgl.
-CN d «* 282 H H H ₁ CO - ^ y ~ NHSO ₁ O- H H -CH ₁ -CN / "\
OHN- 21) H ₁ C- ^ NHSO ₁ O- -CH, H H H -CH, -CN CH, QH ₄ OCH,
dcsgL 2 * 4
285 CI - (^) - NHSO ₁ O- -CH,
H -CH,
-OH, H
H H
H -CH,
-CH ₁ -COCH ₁
desgL dctgl. m H H -a H -QH, -CN dwgl.
detgl.
-C ₁ H ₄ OH
the same 2S7
2 sl
219
290
291
292
291 H
H
-CH>
H
-a
H
H H ₁ QCH ₁ NHSO ₁ O-
HjQ (QH ₁₁ ) NSO ₁ O-
CIC ₁ H ₄ NHSO ₁ O-
HjQOQK ₄ NHSO ₁ O-
HtQNHSO ₁ O-
CH ₁
-CH, H
-CH,
H
-CH,
-a
HtQNHSO ₁ O-
(H ₁ CANSO ₁ O -CH,
H
-CH,
H
H
H
H XXXXXXX -QH,
-QH,
-QH,
-QK,
-QH,
-QH ₅
-QH, -CN
-CN
-CN
-COCHj
d «gl
dogl.
the same

Ήο-ΉΌ-

«HO-

'HO-

Hho'ho'hdJn-

¹ Ht) CHO) N-

'(' H ¹ O) N-

^f H0-

'H «0-

-G

-N H O

VHO (N- ⁴ Ht) -

'HOO ¹ Ht) -
«HO-

'HO-

HO * Ht> T «s» p

■ | »tap

ND-NO-

NO-

NO-

NO-

NO-NO- NO-NO- NO-NO- NO-

NO-NO-

, NO-

NO-ND-

Ήοοο-

NO-

NO-

NO-NO- NO-NO- NO- ¹ HOOO

'HO- • Ht> -

'HO-

¹ HD-'HO-

• ηο- • ηο-ΉΌ-'Ht) -

• Ht) -

ΉΌ-

Ήο-

Ήο-'HD-

'HD-'HO-

'HO-

'Ht) - ¹ H ¹ D-

H
H
H

H
H
H
H
H
H
H

H
H

H
H
H
H
H
H

H H H

H H

«ΗΟ-H H H H

Ο-H

H H

H H H H H H

continuation

Bd-
ipid A, -Br A » H A * H ₁ NSQ ₁ - H QKjHNSQ, - -CH, A ₄ A, B, B, B, -N (CH,), 320 H H -σ H -σ detgl. H iic * (L H H H -CH, -CN -CH ₁ CH ₁ OCH, 321 H H H K dcigl H QH ₁ OQH ₄ SQ, - H H H -CH, -CN -NH (CH ₁ HIGH, 322 H -NO, H H detgL H -CH, H H -CH, -CN -CH, 323 H -CN H H OCH ₁ -NO, H H -CH, -CN -NHCH, 324 H H H H H -NQ, H H CH, -CN -NH (CHj), 325 H H (CHj) ₁ NSQ, - H H H H H -QK, - “CN -CH, 326 H H the same H H H H H -CH, -CN -CH (CH ₁ ), 327 H H desgL K -NO, H H -CH, -CN -N (QH,), 328 H H de * »). H H H H -CH, -CN -NHCH ₁ CHjCN 329 H H H ₁ QSO ₁ O- H H H H -CH, -CN -CH ₁ CHjCH ₁ CH, 330 H H detgl. -NO, H H H -CH ₁ -CN -CK, 331 H desgL H H H H -CH, -CN -N (CH,), 332 H de $ gl. H H H H -CH, -CN -CH, 333 H -NO, tNQ, H -OH, -CH, -CN -NHCH, 334 H -NO, -NO, -OH, H -CH, -CN -N (QH,), 335 H -NO, H -OH, -CH, -CN -CH, 336 H -NO, H -OH, -CH, -CN -NO, -N (CHJ, 337 CHjNHSO, - H H ' H -CH, -CN -CH, 331 dtt | L H -CH, H -CH, -CN -CHjCH ₁ OCH, 339 detjL -CH, H -CH, -CN -N (CHJ, 340 dtt | L H H -CH, -CN -CH.COOQkV 341 H H -CH, -CN detgL 342 H H -CH, -CN QH ₁ COOQH ₄ - 343 H I! -CH, -CN CNCHjCOOQH ₄ - 344 H H -CH, -CN ClCH ₁ COOQH ₄ - 34} H -JN -CH, -CN HjQCOOQH ₄ - 346 H H -CH, -CN H, QCHjCOOQH, - 347 H H -CH, -CN 4-HjCOH ₄ C ₄ COOQH ₄ - 348 H H -CH, • CN 4 ^ IH ₄ QCOOQH, - 349 H H -CH, -CN 2-4-CI ₁ H ₁ QCOOQH.- 3 » H H -CH, -CN C ₁ H ₇ COOQH ₄ - 3Sl H H -CH, -CN CHj = CHCOOQH ₄ - 3S2 H H -CH, -CN

continuation

M-
■ 1 * 1 A, A, A, CH ₁ OCO- -NO, CH ₁ SO, - H CHjSQ, - A. A, B, B ₁ B, 353 -NO, H H H.CCONH- H H -CH, -CN CH ₁ COOCH ₄ OCOc K ₄ - ¹⁵⁴ -σ H -NO, HjCSO ₁ NH- H H -CH, -CN CHjCOOCH ₄ - 35) H H KjCOCONH- H H -Ct ,, -CN C ₄ H ₉ COOCHt- 356 -Cl H H ₁ CSO, - H -α -CjH, -CN CHjCOOCH ₄ - 357 -NO ₁ Il CH ₁ SO ₁ NH- H H -CH, -CN CH ₁ COOCH ₄ - 35t -CN H CH ₄ SO ₁ NH- -α H -CH, -CN CHjCOOCH ₄ - 359 -α H -NO, H H -CH, -CN CIIjCOOCH ₄ - 360 H K -NO, H H -CH, -CN HjCCOOCH ₄ - 361 -Br H -NC, H -NO ₁ -CHjCH ₁ O -CN -CH, 361 « H H -NO, H -Br -CH ₁ CH ₁ Br -CN -CH, 36t b H H -NO, H -Br -CH ₁ CN -CN -CH, 36Ic -Br H -α H K CH ₁ OCH ₁ . -CN -CH, 36Id H H -NO, H -NQ ₁ CH.OCH, -CN -CH, 361 -σ H H H H -CH, -CN -CH, 36If H H H H -CH, -CN Oa 36t ι -NO, H -NO, H H -CH, -CN <> * 36Ib K -NO, H H H -CH, -CN <5 " 36If H -NO, H H -CH, -CN - <Ο " ^0Η 36tj H H H H -CH, -CN Oh 361k -α H H -NO, -CH, -CN _ΗΑο -ρ 3611 -α. H -O K -CH ₁ -CN χΟΗ 361m H H H H -CH ₁ -CN ο- 36In H -NO, H H -CH ₁ -CN "b

The dyes in Table 2 correspond to the Fonnd

D - N =

example O B, -CH, - CN B, 362 6-methox.y-benz-
I hta y / \ 1 vl «9 -CH, —CN -CH ₁ CHjOH 363 6-methylsulfonyl- -CH ₂ CHjOH benzthiazolyl-2 -CH, —CN 364 6-nitro-benzothiazolyl-2 -CH, —CN -CjH, 365 4-phenyl-5-nitro- -CH, ' thiazolyl-2 -CH, —CN 366 S-Nhro-thiazolyl-2 -CH, —CN -C ₁ H, 367 13,5-triaolyl-2 -CH, —CN -CH ₂ CH ₂ CH ₁ OCH, 368 ImidazolyI-2 -CH, —CN - CHtCH ₂ CHjOCl ^ 369 I - M ethyI-5-chloro-benz-
¹ iffiiHsi? I% 1vl * 7 -CH, —CN -CH ₂ CHjCH ₂ OCH, 370 l-Phcnyl-3-mcÜiyl-
nvfa7olvl-7 2-methylphenyl - CN -CHjCH ₂ OH 371 5,6-dimethoxy-benzthia-
7olvl-2 CH ₅ - CN -CH, 372 3-MethyMhiadiazolyl-S -CH, -COCH, -CH, 373 Z-acetyl ^ nitro- -CH, - CN -CH, 374 'H11 tHJf 1 -'
t-McthyI-4-cyan-
Bvra? I> IvI-5 -C ₂ H, - CN 375 ^ Methyl-S-cyano-thiazo-
lvl-2 -CH, —CN -CH, 376 iyi-x
5-EthylsulfonyI- -CH, thiazolyl-2 -CH, - CN 377 l-methyl-4-niUo- -C ₂ H, imidazolyl-5 -CH, - CN 378 6-methoxy-benz-
thia7nlvl- ^ -QH, —CN - CHjCHjOH 379 6-ii-cyanoethylsulfonyl -C ₁ H ₄ benzothiazolyl-2 -QH, - CN 380 6-aminosulfonyl -CH, : benzothiazolyl-2 -QH, - CN 381 4-nitro-thiazolyl-5 -QH, - CN -CH ₂ CHjCH ₁ OCH, 382 ^ -Acctyl ^ nitro
thipnvi-5 3-methoxypbenyl - CN -CH, 383 llllGIIJfl * J
5,6-dimethoxy-benz- -CH ₃ . thiazolyl-2 -CH, - CN ♦ - 384 4-phenylazo-phenyl -CH, - CN -CF ₂ CH ₂ COQH, 385 2-methoxy-4- (4'.nitro- -CH ₂ CHjCOQH, phenylazo) -phenyl -CH, - CN 386 : 4-phenylazo-naphthyl -CH, —CN -CH ₂ CH ₃ CN 387 2-nilro-4- (4'-phenyl- -CH ₂ CH ₁ OH amiuosulfonyl- phenyl) -phenyl -CH, —CN 388 4- (2'.4'-Dinitrophenyl- —CHjCHPH amino) -phenyl -CH, —CN 389 <M4'-acetylamino-
phenyl) -phCT »; i —CHjCHjCN

19Dl

continuation

42

O B, -CH, %; —CN B, -CH, 390 6-dimethylamino » salphonyl-naphyll-2 -CH, —CN -CH, 391 2JUhoxy-naphthyH Pyridyl-3 —CN -C ₂ H, 392 4-phenylazo-phenyI Thienyl-2 —CN -CH, 393 5-nitro-thiazclyl-2 Thienyl-2 —CN -N (CH ₃ ), 394 desgL Thicnyl-2 —CN -C ₂ H ₄ 395 the same Thiazolyl-5 -COC ₂ H, -QH ₇ 396 3-methyl-thiadiazolyl-S Thienyl-2 —CN -C ₂ H ₅ 397 Benzthiazolyl ^ Thiazolyl-5 -SO ₅ CH ₃ -NHCH ₂ CH ₂ OH 398 3-methyl-thiadiazolyl-5 Thiazolyl-5 -NHCH ₂ CH ₂ OC ₂ H, 399 ! dögi- Pyridyl-3 —CN N-piperidyl 400 2 * aoctyl * 4-nitro- Pyridyl-3 —CN -CH,. <01 desgL Pyridyl-3 —CN -C ₂ H ₅ 402 ^ Methyl-S-cyano-
th yes »oil v |> 2 -CH ₂ N-pipcridyl. 403 6-ethoxy-benztbiazolyl-2 Thienyl-2 - —CN -C ₂ H, 404 the same Thienyl-2 -SC ₂ CH, -N (C ₁ H ₅ ) !, 4.5 6-nitro-benzniazolyl-2 Pyridyl-3 —CN N-morpholinyl 406 ; the same Benzimidazolyl-2 —CN -N (CH ₂ CH ₂ CN) !, 407 S-NItro-thiazolyl ^ Furyl —CN -N (CH ₂ CH ₂ CN), 408 l-methyl-4-cyano-
DvnizoIvl-5 Thienyl-2 —CN -CH ₂ CH (CH,), 409 6-methylsultonyl —CN benztbiazolyl-2 Thienyl-2 -SO ₂ QH ₅ -CH ₂ CH ₁ OCOCH, 410 6-Cyanoätbylsulfonyl- benzthiazolyl-2 Thienyl-2 —CN -CH ₂ CH ₂ COOCH ₃ 411 \ the same Thiazolyl-5 -C ₂ H ₅ 412 1-methyl imidazolyl-2 3-methylthienyl-2 - CN -N (CH ₂ CH ₂ OCOCH,), 413 Thiazolyl-2 3-methylthienyl-2 -COC ₄ H ₅ -CH ₃ 414 the same -COOC ₂ H ₅ -CON (C ₂ H ₅ ) !,

Example 415 The dye of the formula

CH,

45

CN

OH

Claims (3)

; Patent claims: J. Verfahrrr. fen for the production of Azofarbstof- SS, dadurc J ^ indicates that an amine .the >>:. ·. ? r »el I '< R: - NH ₂ Ο) wherein Ri loading the radical of a diazo component to indicated, is diazotized and coupled with a compound of Formein (Π) where R _{2 is} a cyano or /. cyano group, R is an optionally substituted by Cl, B ΓΝ or alkoxy alkyl group with 1 to 6 carbon atoms or an optionally substituted aryl or heterocyclic group and R _{4 is} an optionally substituted hydrocarbon group or an amino group mean, where the radicals R _t to R ₄ contain no sulfonic acid groups and radicals capable of attachment of a proton as substituents, to form azo compounds of the formula III (UI) OH R ₄ couples, wherein R ,, R ₂ . R, and R _{4 have} the meanings given. 2. The method according to claim i, characterized in that now kup ^ -itüisifihigc compounds of the formula (II) verreist, wherein R, an optionally ^{substituted by CW -} U or bromine atoms, Cyaa or Alkoxygnipp.-n alkyl radical with I to 6 Carbon atoms, one optionally with chlorine or fluorine atoms. Hydroxy, alkyl, alkoxy, alkylamino, Dia Iky! Amino. Nitro, cyano, acyl. Acyloxy or acylamino groups substituted phenyl, a naphthyl, alkoxynaphthyl. Thionyl, methylphenyl, benzthiazolyl, methoxybenzihiazolyl, acylbenzlhiazolyl, acyloxybenzothiazole. Furyl, thiazolyl, pyridyl, imidazolyl or benzimidazolyl radical, R _{4 is} an optionally substituted alkyl or alkenyl group with 1 to 10 carbon atoms, but one which is free from protonizable groups, and one optionally substituted but protonizable Groups free phenyl radical or a radical of the formula ^ R ₉ - N Rj is a WusscrstofTatom or one of the meanings of R ₆ and R _{4 is} an optionally substituted hydrogen radical with 1 to 8 carbon atoms or R ₃ and R «together with the nitrogen atom attached to them is a helerocyclic ring system with up to 5 carbon atoms. 3. Process for dyeing or printing fibers or fiber material made of fully or semi-synthetic, hydrophobic, high molecular weight organic substances, characterized in that .rt? r dyes of the formula (IH) according to claim 1 are used.