BE574446A - - Google Patents

Description

       

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  Monoassic dyes, their preparation and applications
The present invention relates to novel monoazo dyes which work well on wool in a neutral or weakly acidic bath and then give very pure dyes having very good lightfast and wet fastness properties. The invention also relates to a process for preparing these new dyes, their use for dyeing natural and synthetic polypeptide fibers and finally materials solidly dyed with these dyes.



  The Applicant has found that interesting monoazoic orange, yellowish-red or bluish-red dyes were obtained by coupling in the medium.
 EMI1.1
 2-amino-benzene-1-aulfonyl acid a compound

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 diazotized comprising the sulfonyl substituent -SO2R in which R represents a hydrocarbon or aryloxyl residue or an organic amine residue and in which all the organic residues may also carry various substituents, with a
2-amino-naphthalenesulphonamide coupling in position 1, the sulphonamide nitrogen atom of which bears a sulphonated organic residue as a substituent and the naphthalene ring of which optionally contains a hydroxyl group in position 8.



   The residue R is either a hydrocarbon residue of the aliphatic, araliphatic or aromatic series, or a secondary amine residue or more especially a tertiary amine, the substituents of this amine residue possibly being aliphatic, cyclo- aliphatic, araliphatic or aromatic.



  The residue R can, moreover, be an aryloxylic group.



  As substituents capable of being found both in the benzene ring carrying the anine group and in the residue R, one can consider the usual substituents in azo dyes, for example halogens, nitro, alkyl, alkoxylic, aryloxylic, alkylcarbonyl groups, arylcarbonyls and acylated amino groups. Among the diazotization components bearing substituents on the amino-benzene ring, those which contain nucleophilic substituents such as alkyl groups, ether groups or acylamine groups are preferred.



   The following amines give, for example, o-diazo-benzene-alkyl-, aralkyl- or-aryl-sulfones which can be used according to the invention: 2-amino-phenyl-1-methyl- or -1-ethyl-sulfone, 2-amino-phenyl-1-benzyl-, -4'-chloro-
 EMI2.1
 benzyl- or -3 '.4'-dichlorobenzyl-sulfone, 2-anino-phenyl-1 - menaphthyl-sulfone, 4-ehloro-2-aminophenyl-1-benzyl-sulfone, 2-aminophenyl-1- n-octyl-sulfone, 2-amino-1.1t-diphenyl-sulfone, ç'-methyl-2-amino-1.1'-diphenyl-sulfone, 4'-chloro-2-amino-1.1 '- diphenyl-sulfone, the 4.4 '

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 EMI3.1
 -dichloro-2-anino-1.l'-diphenyl-sulf one, 2-amino-phenyl 1- -naphthyl-sulfone, 4- or 5- or 3'-acetylamino-2-anino- 1.l ' -diphenyl-sulfone as well as the corresponding 4- or 5- or 3'-propionylan.ines and benzoylaninated derivatives and 4- or 5- or 3'-carbomethoxyamino-,

   carboamyloxyamino-, carbocyclohexyloxyamino-, carbobenzyloxyamino- or carbophenoxyamino-2-amino-l.l'-diphenyl-sulfone.



   In the o-diazo-benzene-sulfonamides which can be used according to the invention, the hydrogen atoms of the amidic group can be replaced by aliphatic, cycloaliphatic, araliphatic or aromatic residues. Such diazotization components are for example: N-dimethyl-amide of 2-amino-benzenesulfonic acid, N-diethyl-amide of 2-amino-benzenesulfonic acid, N-dibutyl - 2-amino-benzenesulfonic acid amide, 2-amino-benzenesulfonic acid N-2'-carbo-xyphenyl-amide, N-ethyl-N-phenyl-amide '2-an ino-benzene-sulfonic acid, 2-amino acid N-methyl-N-4'-chlorophenyl-amide
 EMI3.2
 benzene-sulfonic acid, N-methyl-N-3'- ° '-di.chlorophGny1-amide of 2-amino-benzene-sulfonic acid,

   2-amino-benzenesulfonic acid N-Óthyl-N-2'-methyl-phenyl-amide, N-methyl-N-4'amyl- or -4'-butyl-phenyl-amide 2- acid
 EMI3.3
 amino-benzene-sulfonic acid, N-methyl-N- i, -hydroxy-ethylamide
 EMI3.4
 1) / 2-amino-benzene-sulfonic acid and q-mA-thyl-1,11- * èY '1 methoxypropylamide 2-amino-benzenesulfonic acid
 EMI3.5
 5-amvl-2-amino-benzenesulfonic acid N-methyl-N-phenyl-amide, 2-anino-benzenesulfonic acid N-methyl-N-cyclohexylamide, N-dicyclohexyl 2-Amino-benzenesulfonic acid amide, 2- Acid N-methyl-N-xenyl-amide
 EMI3.6
 amino-benzene-sulfonic acid, N-methyl-N-4 .'-phenoxyphenyl-amide of 2-amino-benzene-sulfonic acid,

     2-amino-benzene-sulfonic acid N-methyl-N-naphthyl-amide,

 <Desc / Clms Page number 4>

 
 EMI4.1
 2-an.ino-benzenesulfonic acid N-methyl-N- B-naphthyl-amide, 2-amino-benzene-sulfonic acid N-methyl-N-benzyl-amide, N- 2-amino-benzenesulfonic acid benzyl-N-phenyl-amide and 2-amino-benzenesulfonic acid N-ss - (ar) -tetrahydronaphthyl-amide.



   In the aryl esters of o-diazobenzenesulphonic acids which can be used according to the invention, the residue R linked to the sulphonyl group represents an aryloxyl group of the benzene or naphthaléniaue series which may bear other substituents customary in azo dyes. One can take, for example, the diazonium compounds of the following amines:

   2-Amino-benzene-sulfonic acid phenyl ester, 2-amino-benzene-sulfonic acid 2'- or 4'-methyl-phenyl ester, 41-amyl-phenyl ester 2-amino-benzenesulfonic acid, the 3'.4'- ester
 EMI4.2
 2-Auino-benzenesulfonic acid dichloro-phenyl, 2-amino-benzenesulfonic acid 2'- or 4'-cyclohexyl-phenyl ester, 2'- or 4'- ester 2-amino-benzenesulfonic acid xenylic acid, the 2'- or 4'-phenoxy-pheny- ester
 EMI4.3
 2-an.ino-benzene-sulonic acid lic, 2-amino-benzenesulfonic acid 4'-acetyl-, -propionyl-, -butyryl- or -chloracetyl-amino-phenyl- ester ,, the 4'-carbomethoxyamino- ester,

     -carbobenzyloxyamino- or -carbocyclohexyloxyamino-phenylic acid 2-amino-benzene-sulfo-
 EMI4.4
 nique, itestel <> (- or l3 -naphthyl of 2-Em-'Lnobenzene-sul¯fonic acid and the ester B - (ar) -tetrahydronaph1; ylic of 2-aino-benzne acid = sulfonisne.



  , "The diazotization compounds which can be used according to the invention can be obtained, by known methods. Amides and esters of sulfonic acids, from (ffo; .. nitrô-bÈmzè-sulfhalide6 by condensation., ... ..- '......... - <. .... -'

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 with amines or phenols, then reduction of the nitro group to an ine group. The alkyl sulfones are prepared by
 EMI5.1
 example by alkylation of o-nitro-benzenesulfinic acids and aryl-sulfones by condensation of aryl-sulfinic acids with nitro-benzenes containing a mobile halogen, after which, in this case too, the nitro group is reduced to amino group.



   In the preferred diazotization components there are no other substituents on the amino-benzene ring or, at least, no negative substituent. With such components, especially when the sulfonyl substituent '-SO2R is a sulfonamide group, dyes having particularly good lightfastness are obtained.



   The coupling components that can be used according to
 EMI5.2
 the invention are substituted 2-amino-naphthalene-sulfamidas which can be copulated in position 1. One can consider above all the derivatives of 2-amino-naphthalene-5-, -6- or -7-sulfonic acids. The coupling components are characterized in that they carry as a substituent, on the sulfonamide nitrogen atom, a sulfonated organic residue, while
 EMI5.3
 The pta1éque nucleus:, l-: even does not carry a free sulfonic acid group. This nucleus can however carry other nonionogenic substituents, such as halogens, alkoxylic groups and also, in a suitable position, more secially in position 8, a hydroxyl group.

   The rest
 EMI5.4
 -; ôrqúe; - 'Sufôné. -.pêut -ap-pE # ten1ït -à the aliphatic series, .J 'àràÎÀ9hùtiÀé / G "OÙ aromatic' and; in the latter case, it is' i'â'lilg, i3;., rie-rërï: ïnepas more than two benzene rings- '..-.-' .., g>,: \ ": '...



  .qÇÔ41 -P -: "'id1té .colorants vis-à-vis alkalis, it i .. f4É) @ QU # flitle, -qlq ¯the two. hydrogen atoms of the group"' rv.l..d, iqu'é: so3, ett cbt ... It is then advantageous that it;: e (: r & i: Je;, té.: ¯Órgàm9-ue, an aliphatic residue,

 <Desc / Clms Page number 6>

 unsulfonated araliphatic or cycloaliphatic. Preference is then given to lower alkyl groups, more particularly when the sulfonated organic residue is a high molecular weight alkyl residue or an aralkyl or aryl residue.

   As examples of coupling components which can be used according to the invention, we may cite the 2-amino-naphthalene compounds which bear in position 5-, 6- or 7-
 EMI6.1
 a group of N- (u-sulfo-ethyl) -N-methyl-sulfonamide, N- (4-sulfo-benzyl) -sulfamide, N- (4-chloro-2-sulfobenzyl) -sulfamide, N- ( 4-sulfo-benzyl) -N-methyl-sulfonamide, N- (ss-sulfoethyl) -N-benzyl-sulfonamide, N- (4-sulfo-benzyl) -N-benzyl-sulfo-famide, N- ( 4.-Sulfo-phenyl) -N-methyl-sulfonamide, N- (3-sulo-
 EMI6.2
 phenyl) 'LN-raethyl-sulfonamide, N- (4-sulfo-phenyl) -N-ethyl- or N-butyl-sulfonamide, N- (4-sulfo-benzyl) -N-phenyl-sulfBmide, N- (4 -sulfo-phenyl) -N-benzyl-sulfonamide, N - 7-sulfo-naphthyl- (2) '-sulfamide, N- 7-sulfo-naphthyl- (2) 1 -N-methyl-sulfide or N- [ 4-sulfo-naPhtyl- (1)] -N-me "thyl-sulfanide.

   Among the coupling components for which the naphthalene ring bears other substituents, particularly interesting are the 2-amino-8-hydroxy-naphthalene compounds which bear in position 6 one of the sulfonamide groups listed above.



   The coupling components which can be used according to the invention are new bodies which can be prepared, for example, as follows: after acylation of the
 EMI6.3
 When formed and any hydroxyl groups present, the 2-amino-naphthalene-sulfonic acids are converted with phosphorus halides into the corresponding sulfo-halides. The latter are condensed with primary or secondary amines. sulfonated to obtain the corresponding acylamino-naphthalene-sulfonamides in which

 <Desc / Clms Page number 7>

 the acylanine substituents and the acyloxylic substituents optionally present of the naphthalene nucleus are then hydrolyzed.



   Among the coupling components, those which are of interest for the preparation of orange dyes according to the invention are primarily 2-amino-naphthalene-7-sulfonamides, and those which are of interest for the preparation of red dyes according to the invention. the invention are in the first place 2-amino-8-hydroxy-naphthalene-6-sulfonamides.



   Because of the good wet fastness properties of the dyes which they allow to obtain, the coupling components are preferred which bear on the sulfonamide nitrogen atom an alkyl residue, especially a lower alkyl residue, and a residue sulfonated aryl, especially a sulfonated phenyl or naphthyl residue.

   Therefore, the most interesting dyes of the present invention derive from diazotization components whose benzene ring does not bear any other substituent except nonionogenic nucleophilic groups, and from 2-amino-naphthalene-7-sulfonamides. as well as 2-amino-8-hydroxy-naphthalene-6-sulfonamides containing a tertiary nitrogen atom
The diazotization of the o-amino-benzene-sulfonyl compounds which can be used according to the invention is carried out according to the usual methods, either in organic solvents, for example in acetic acid or in formic acid, with sodium nitrite in the presence of mineral acid, or in concentrated sulfuric acid with nitrosyl-sulfuric acid.



  To couple the sulfo-alkyl or sulfo-aryl amides of 2-amino-naphthalene-sulfonic acids coupling in position 1, it is advisable to use more or less acidic aqueous solutions of their alkali salts. It is often advantageous

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 to operate in the presence of water-soluble organic dissolving auxiliaries such as, for example, ethyl alcohol or dioxane.



  The azo dyes prepared according to the invention are in general isolated in the form of their alkaline salts, for example in the form of lithium, potassium or sodium salts.



  In this state they form orange, red to purple powders which easily dissolve in hot water.



  Already in neutral baths containing ammonium sulphate, they dye the natural and synthetic polypeptide fibers, in particular wool, with a total exhaustion of the baths, giving orange, yellowish red to bluish red shades, very pure, remarkably uniform and strong in the wet.



   But they can also be used, with the same success, for. dyeing in an acid bath, for example in an acetic bath. The wool dyes of the new dyes are distinguished by very good lightfastness, irreproachable alkali fastness and very good wet fastness properties, more particularly by their fastness to washing, to fulling and to seawater. .

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   The following examples illustrate the present invention without in any way limiting its scope. The parts referred to in these examples are parts by weight.



  EXAMPLE 1:
Body of formula 1 attached.



   39.8 parts of 2-amino-benzene-1-sulfonic acid 4'-carbobenzyloxyamino-phenyl ester are suspended in 180 parts of glacial acetic acid, the solution is produced by adding dropwise. 25 parts of 30% hydrochloric acid drop by drop and, at 5 ° C., dinitrogenate by rapidly adding 6.9 parts of sodium nitrite to 20 parts of water.



  At 2-5, the yellowish diazo solution is poured into an acetic suspension of 42.2 parts of 2-amino-8-hydroxy-naphthalene-6- N-ethyl-N-4'-sulfophenylamide. sulfonic acid and 25 parts of sodium acetate crystallized in 500 parts of water and 500 parts of ethanol. Copulation occurs immediately and the mixture turns red. After stirring for 8 hours at 5-10 hours, the mixture is heated to 80, the acid is partially neutralized by dusting 80 parts of sodium carbonate, the dye which has precipitated out is filtered off by suction, washed well with a sodium carbonate solution. 2% sodium chloride and dried.



   With this mono-azo dye, in the presence of ammonium sulphate, the wool is dyed in a neutral or weakly acidic medium, with good exhaustion of the bath, in pure bluish-red shades, very uniform, solid in the light and in the wet .



  EXAMPLE 2:
Body of formula 2 attached.



   Diazotized at 5-10, with 6.9 parts of sodium nitrite, 31.9 parts of the 4'-amylphenyl ester of 2-aminobenzene-1-sulfonic acid in 180 parts of acetic acid

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 glacial and 25 parts of concentrated hydrochloric acid. With stirring, at a temperature of 2 to 5, the diazo solution diluted with ice-cold water is gradually introduced dropwise into an acetic suspension of 40.8 parts of N-methyl-N-4'-. 2-amino-8-hydroxy-naphthalene-6-sulfonic acid sulfophenylamide in 400 parts of ethanol and 300 parts of water. The mono-azo dye which is then formed precipitates in the form of a red powder.

   Stirred for several more hours at 5-10, then heated to 60, partially neutralized the acid by dusting 50 parts of sodium carbonate, the red precipitate is filtered off and dried. In the sodium salt state, the colorant is in the form of a red-brown powder which dissolves in hot water giving a bluish-red color. He dyes the wool in a bath. Containing 5% boiling ammonium sulphate, pure bluish red shades, light solid, fuller and wash solid.



  EXAMPLE 3:
Body of formula 3 attached
32.5 parts of 2-amino-benzene-1-sulfonic acid 4'-xenyl ester are dissolved in 200 parts of glacial acetic acid with 20 parts of concentrated sulfuric acid and nitrogenated at 5-10 by adding dropwise 6.9 parts of sodium nitrite in 15 parts of water. At 0-5, the diazo solution diluted with ice-water is poured into an acetic suspension of 40.6 parts of N-ethyl-N-4'-sulfophenyl-amide of 2-amino acid. -naphthalene-6-sulfonic acid in 500 parts of water. Stirred for several hours at 0-5 then reheated to 60, 120 parts of sodium chloride are introduced, the dye which has precipitated is filtered off and dried.

   It dyes wool, in a neutral or weakly acid bath, in the presence of ammonium sulphate, in orange shades

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 light and wet solids, EXAMPLE 4:
Body of formula 4 attached.



   33.4 parts of 5-carbethoxyamino-2-amino-4'-methyl-1.l'-diphenylsulfone are dissolved in 150 parts of glacial acetic acid with 40 parts of concentrated hydrochloric acid and nitrogen is 5-. 10 by adding dropwise 6.9 parts of sodium nitrite in 20 parts of water. The yellow diazo solution was stirred for a further 1 hour at 0-5, then the excess nitrous acid was destroyed. At 2-5, the diazo solution is poured into an acetic suspension of 48.4 parts of N-benzyl-N-4'-sulfophenyl-amide of 2-amino-8-hydroxy-naphthalene-6-sulfonic acid in 500 parts of ethanol and 300 parts of water. Stirred for several hours at 0-5, then heated to 60, 100 parts of sodium chloride are introduced, the dye which has precipitated is filtered off and dried.

   The dye dyes the wool, in a neutral or weakly acid bath, in the presence of ammonium sulphate, in pure bluish red shades. solid to light and alkalis.



  EXAMPLE 5:
Body of formula 5 attached.



   33.6 parts of 2-amino-benzene-1-sulfonic acid dicyclohexyl-amide are dissolved in 150 parts of glacial acetic acid with 19 parts of concentrated sulfuric acid and; at 10-15, with good stirring, dinitrogenated with a solution of 6.9 parts of sodium nitrite in 15 parts of water. 50 parts of ice are gradually introduced, then the yellowish diazo solution is poured into a sodium salt solution of 42.2 parts of N-ethyl-N-3'-sulfophenyl-amide of 2-amino-8 acid -hydroxy-naphthalene-6-sulfonic acid and 25 parts of sodium acetate crystallized in 600 parts of water. The

 <Desc / Clms Page number 12>

 copulation occurs immediately and a red coloration appears.

   Stirred for 6 hours at 0-10, then the acid is partially neutralized by sprinkling 30 parts of sodium carbonate, 100 parts of sodium chloride are added, the dye which has precipitated is filtered off, washed over filter until neutral with 2% aqueous sodium chloride solution and dry at 80. In the sodium salt state, it is in the form of a brown powder which dissolves in hot water giving a bluish red color.



   The dye dyes wool when boiling in a 5% ammonium sulfate bath in regular bluish-red shades, pure, very light fast and wet.



   EXAMPLE 6:
Body of formula 6 attached.



   33.8 parts of N-benzyl-N-phenylamide are diazotized with 2-amino-benzene-1-sulfonic acid under conditions analogous to the conditions described in Example 5 and copulated, at 0-5, with a suspension of 40.6 parts of 2-amino-naphthalene-7-sulphonic acid N-ethyl-N-4'-sulfophenylamide and 40 parts of sodium acetate crystallized in 400 parts of ethanol and 300 parts of water. Copulation also occurs early and an orange coloration appears. The mono-azo dye which is then formed immediately precipitates in the form of an orange powder.

   The mixture is stirred for several hours at 0-10, the acid is partially neutralized with 80 parts of sodium carbonate, the dye which has precipitated is filtered off by suction, washed on the filter until neutral with an aqueous solution of 2. % sodium chloride and dried.



   It comes in the form of a brown powder, it dissolves in hot water giving an orange color and

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 it dyes wool, when boiling, in a bath containing ammonium sulphate, in orange shades, pure and regular, solid in the light and in the wet.



  EXAMPLE 7:
100 parts of groin are suitably wetted, which are then introduced at 40 into a dye bath containing, in 3000 parts of water, 2 parts of the mono-azo dye which can be prepared according to Example 5 and 10 parts of salt of Glauber. Then it is brought to the boil in 45 minutes and the wool is boiled for 1 1/2 hours, stirring well.



  During this time the dye rises almost completely on the wool. A very regular, pure, bluish-red wool dye is obtained, which is distinguished by very good solidity properties.



   Also good dyes on wool are obtained using an acid dye bath, for example in the presence of 1 to 2 parts of 40% acetic acid.



   With the dyes from all the other examples you can dye wool in the same way.



   The following table contains other monoazo dyes according to the invention which can be prepared by the method described in Examples 1 to 6 using the corresponding amounts of diazotization components and coupling components.

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  BOARD
 EMI14.1
 
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 EMI14.2
 He and 30.5 îEster 4'-tert. : 42.2: N-ethyl-N-4'-sulfo bluish red i: 2-amino acid ibutyl-phenyl-iphefiyl-amide- 2-amino-8-s acid: 1 sno-benzene-1-sulfb shydroxy-naphthalene-1. snique. s6-sulfonic.
 EMI14.3
 12 1 33.1 tEster 4'-cyclo- 1 42.2 1 d d. : i rhexyl-phenyl "1 S Ide 2-amino acid ino-benzene-1-sul- 'r' i 1 3 fonic. 'r -r! 1: 1 to 3 r 24.9 Phenyl ester t 45 , 8 to N-methyl-N- [7-sulfo-1 d:

   It is 2-tnaphthyl- (2) J-amide and Samino-benzen-1-: 2-amino-: i -sulfonic acid. 18-hydroxy = nâphthalenet i s6-sulfonic acid. s
 EMI14.4
 
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 EMI14.5
 : 4 1 32.5: 4'-xenyl ester: 40.6 iN-ethyl-N-4'-sulfo-orange s: 2-ami- acid: si-no-benzen-1-su lfo phenylamide -: 2-amino- acid,: i Inic. inaphthalene-7-sulfo- '::
 EMI14.6
 
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 EMI14.7
 s5 i 1 29.9 1 sEster -naphthyli- 40.6: dO d:
 EMI14.8
 
<tb>: <SEP> that, <SEP> of <SEP> acid
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 EMI14.9
 s: 2-amin-benzene-i-sulfonic acid, at 6 '1 1 29.9 lEsteà / -naphthyli- 1' '40.6:' jdd::: as 2-: amino-benzen-1 acid - 1
 EMI14.10
 
<tb> sulfonic
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 EMI14.11
 17 1 32.5: 2'-Xenyl ester 40.8 s N-methyl-N-3'- bluish red i ide 2-amino-i sulfophenyl-amide! ino-benzen-1-: 2-amino- acid;

   i isulfoniqpe. 18-hydroxy-naphthalene-1-ine-6-sulfonic acid.
 EMI14.12
 s8 333,1: Ester 2'-cyclo- '40, 8 d d8:
 EMI14.13
 
<tb> ': hexylphenyl:
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<tb> '; from <SEP> the acid <SEP> 2-ami- <SEP>: <SEP>;
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 EMI14.14
 : tno-benzeno-1- 'r':
 EMI14.15
 
<tb> sulfonic. <SEP>:
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 i::! #######################: ########## t: 9 t s1,8: Ester3'.4'- di- 40.8; 1 N-methyl-N-3'-sul-: red: -: chlorophenyl ": bluish fophenylamide
 EMI15.3
 
<tb>: from <SEP> the acid <SEP> 2- <SEP> ':

   <SEP> acid <SEP> 2-amino-8- <SEP> @
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 EMI15.4
 1: amino-benzene-1-: hydroxy-naphthalene-iosulfonic acid. ':': 6-sulfonic ..: ts * i101 s 30.5 ïEsterM- (ar) - * Q: t ": 43.4 * <Nn-butyl-N-4'-sul- orange i ttetra-hydronaphty - Acid tick sfophenylamide:: 2-amino-s: 2-amino-benzene-1- "tnaphthalene-5-sulfo- acid
 EMI15.5
 
<tb> sulfonic <SEP> nic.
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 EMI15.6
 : 11: 36.6 '': 5-benzoylamino-2- vs 42.2 gN-ethyl-N-4'-sulfo bluish red 1: tamino-4'-methyl-iphenyl-amide of 1 II. 1 ' -diphenyl- 1 ": 11 acice 2-amino-8- -1 t -: sulfone. ':.: hydroxy-naphthalene-' ios i6-sulfonic,
 EMI15.7
 i121 39.6: 5-carbobenZ²loxy- 1 42.2: dO d i samino-2-amino-4'- s: i smethyl-1.1'-diphe-! onylsulfone, s
 EMI15.8
 ! 13 40.85 s4-carbocyclohexyl- 42.2: N-methyl-N-4'-sUlfo-: d: toxyamino-2-amino =: benzylamide from a-:

   04 '-chloro-1, 1' -d1- 1cide 2-amino-8-hy- tphenyisulfone. idroxy-naphthalene-6-
 EMI15.9
 
<tb> sulfonic
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 EMI15.10
 ; 14 35.2 s2-gmino-3'-benzoyl-s 39.2, N-methyl-N-3'-sulfo-, red orange 1: ': amino-1.1'-diphenyl-: phenylamide! : sulfone. : 2-amino- acid:: naphthalene-7-sulfo-:
 EMI15.11
 
<tb> picnic
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 EMI15.12
 1 lsi 23.3 t2-amino-l.l'-di-48.4 sN-benzyl-N-4'-sulfo-bluish! i phenyl sulfone, i phenyl amide: 2-amino-8- i s-hydroxy-naphthalene-s: t s6-sulfonic acid.
 EMI15.13
 : 16: 31.3 -: 2-amin0-3l-sulfot 484 1 dO dO .s :, 11.1'-dipheny1- '' t i isulfone. t. ':
 EMI15.14
 ! 17 27.6 M-ethyl-N-phenyl-45.8 ¯N-methyl-N-4'-sulfo-i d: the acid amide ;;; 1. -naphthy1amide from:

   : 2-amino-benzen-1- ": ': 2-amino-8.-: sulfonic acid. - t-shydroxy-naphalene-
 EMI15.15
 
<tb> @ <SEP>: 6-sulfonic.
<tb> @ <SEP> t
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 <Desc / Clms Page number 16>

 
 EMI16.1
 S S. t Î 'i 1 t' RP: Parts' Component of: Parts: Component of: Color of the f - tdiazotization. "':

   copulation, 'dye on
 EMI16.2
 
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 EMI16.3
 <18 33.1 iN-methyl-N-3 '. 4'- 45.8 tN-methyl-N-4'-sulfo-sbluish red sdichloro-phenyl-S -naphthylamide da, acid amide 1 II' 2-Amino-8- 't2-amino-benzene-1-Shydroxy-naphthalene-t-sulfonic acid. i6-sulfonic. '
 EMI16.4
 19 33.8 tN-benzyl-N-phenyl-40.8 tN-4'-sulfobenzyl-red. acid amide 2- acid tamide:

  2-.amino-benzene-1-samino-8-hydroxy-tsulfonic. snaphthalene-6-sulfo-
 EMI16.5
 
<tb> fuck.
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 EMI16.6
 1201 33.8 1 d i 40.8 sN-methyl-N-3'-sulfo-t d
 EMI16.7
 
<tb> @ <SEP> @ <SEP> iphenylamide <SEP> from <SEP> @
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<tb> @ <SEP>. <SEP> 2-amino-8- acid
<tb>
 
 EMI16.8
 '1 -1 thydroxy-naphthalene-
 EMI16.9
 
<tb> 6-sulfonic
<tb>
<tb>
<tb> 21 <SEP> 33.8 <SEP> d <SEP> 1 <SEP> 39.2 <SEP> 1N-4'-sulfobenzyl- <SEP> orange
<tb>, acid <SEP> amide <SEP>
<tb> @ <SEP> t2-amino-naphthalene-
<tb>
 
 EMI16.10
 , ':. t7-sulfonic,
 EMI16.11
 t221 29.2 tN-2'-carboxyphenyl-t 49.8 1N-benzj-1-N-4'-sulfo-red yellowish i2-amino acid ibenzylamide iamide = benzen-1-! 2-amino-8-ssulfonic acid.

   Hydroxy-naphthalene-t 56-sulfonic acid,
 EMI16.12
 
<tb>
<tb>
<tb>
 
 EMI16.13
 t! 31 35, i sN-ethyl-N-4'-sulfo-s t 49.8 d. d * ""
 EMI16.14
 
<tb> phenylamide <SEP> from
<tb>
<tb> tl'acid <SEP> 2-amino-
<tb>
 
 EMI16.15
 "tbenzene-1-sulfoni-
 EMI16.16
 
<tb>: that.
<tb>
 
 EMI16.17
 : 24t 29.0 SN-ethyl-N-2'-, 40.8 iN-sttethyl-N-4'-sulfo-irouga bluish: imethyl-phenyl-iphenylamide of 2-, 11-acid tamide -amino-8- oamino-benzen-1-t-hydroxy-naphthalene-osulfonic, o6-sulfonic, i
 EMI16.18
 35.2, N-benzyl-N-2'-, 40.8-, d. d.
 EMI16.19
 
<tb> Imethyl <SEP> phenyl <SEP> amide <SEP>
<tb> tde <SEP> acid <SEP> 2-amino-
<tb>
 
 EMI16.20
 tbenzene-1-sulfoni-
 EMI16.21
 
<tb> that
<tb>
 

 <Desc / Clms Page number 17>

 
 EMI17.1
 ,:. 1. : t "::

   
 EMI17.2
 
<tb> N <SEP> Parts <SEP> Component <SEP> of <SEP> Parts <SEP> Component <SEP> of <SEP> Color <SEP> of <SEP> the
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> @ <SEP> @ <SEP> dialing. <SEP>: <SEP> @ <SEP> copulation. <SEP>: dyeing <SEP> on <SEP>: <SEP>
<tb>
<tb>
<tb>
<tb> wool.
<tb>
 
 EMI17.3
 



  ZI: 1 1: 261 37.8: 4'-carbo- 1 40.8 ester: N-methyl-N-4'-sulfo-: bluish red 1: samyloxyamino-pheny-iphenylamide of 1 ilic acid ' 2-Amino-8--: se 1: 12-Amino-benzne-1-:: hydroxy-naphthalne-i 1 isulfonic, i: 6-sulfonic acid.
 EMI17.4
 
<tb> 27 <SEP> 39.8 <SEP>: Ester <SEP> 3'-carbo- <SEP>: <SEP> 40.8 <SEP>: <SEP> d <SEP> d '
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> @ <SEP>: benzyloxyamino-ph- <SEP>: <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> @ <SEP> @ <SEP>: <SEP> nylic <SEP> of <SEP> acid <SEP>: <SEP>
<tb>
 
 EMI17.5
 1 1 12-amino-benzen-1- 1 1 1 i sulfonic, 1
 EMI17.6
 : 281 39.8: d. : 40.6 sN-ethyl-N-4'-sulfo orange
 EMI17.7
 
<tb> @ <SEP> @ <SEP> @ <SEP> phenylamide <SEP> from <SEP> aci-
<tb>
 
 EMI17.8
 :::: from 2-amino-naphthalè-:

   
 EMI17.9
 
<tb>: ne-6-sulfonic.
<tb>
<tb>
<tb> 29 <SEP> 34,05 <SEP>: Ester <SEP> 4'-chloraceous- <SEP>: 42,2 <SEP>: N-ethyl-N-4'-sulfo- <SEP>: < SEP> Red <SEP> bluish
<tb> tylamino-phenyli- <SEP>: phenylamide <SEP> of <SEP> acid
<tb>: <SEP>: that <SEP> of <SEP> acid <SEP> 2- <SEP>: of <SEP> 2-amino-8-hydro- <SEP>: <SEP>
<tb>
 
 EMI17.10
 : aminobenzene-1-sul-. : xy-naphthalene-6-sul-:
 EMI17.11
 
<tb>: <SEP> fonic <SEP>: fonic ..
<tb>



  @
<tb>
<tb>: <SEP> 30: <SEP> 36.8 <SEP>: <SEP> Ester <SEP> 4'-benzoyl- <SEP>: 42.2 <SEP> d <SEP> d
<tb>: amino-phenyl <SEP> ... <SEP>
<tb>



  @ <SEP>: <SEP>: from <SEP> the acid <SEP> 2-amino-
<tb>
 
 EMI17.12
 1:: benzen-1-sulfoni-::
 EMI17.13
 
<tb>: that ....
<tb>
<tb> @
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 31 <SEP> 34.1. <SEP>: Ester <SEP> 4'-phenoxy <SEP>: 42.2 <SEP> d <SEP> d <SEP> @
<tb>
<tb>
<tb>: phenyl <SEP> from <SEP> a- <SEP> ... <SEP>
<tb>
<tb>
<tb>



  : <SEP> cide <SEP> 2-aminobenz- <SEP> ... <SEP>
<tb>
<tb>
<tb>



  .. <SEP>: ne-1-sulfonic.
<tb>
 
 EMI17.14
 i32: 33.6: 3'-Carbetho- ester: 44.4: N-7'-sulfo- -naph-: dO
 EMI17.15
 
<tb>: xy-aminophenyl <SEP>: <SEP> acid <SEP> tylamide <SEP>: <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> @ <SEP>: from <SEP> the acid <SEP> 2-amino- <SEP>: <SEP>: 2-amino-8-hydroxy- <SEP>. <SEP>
<tb>
 
 EMI17.16
 :: benzene-1-sulfoni- naphthalene-6-sulfo-
 EMI17.17
 
<tb> @ <SEP>: that. <SEP> fuck.
<tb>
 
 EMI17.18
 t ..



  : 33z 33.8: N-methyl-N-4 '.- xenyl-: 42.2 = N-ethyl-N-4r sulfodo
 EMI17.19
 
<tb> @ <SEP>: amide <SEP> of <SEP> acid <SEP>: <SEP> phenylamide <SEP> of
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 2-aminobenzene-1- <SEP>: <SEP> 2-amino-8- <SEP>: <SEP> acid
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> @ <SEP> sulfonic <SEP>: <SEP>: hydroxy-naphthalene- <SEP>. <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> @ <SEP>: 6-sulfonic ..
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
 
 EMI17.20
 



  : 34: 32,, 45. : 2-amino-3'chlorace-: 42.2 "o,:.:: Tylamino-1.1, I- t 1;: diphenyl-sulfone:.:
 EMI17.21
 
<tb> @
<tb>
<tb>
<tb>. <SEP>: <SEP> .... <SEP>
<tb>
 

 <Desc / Clms Page number 18>

 
 EMI18.1
 
<tb> N <SEP> Parts <SEP> Component <SEP> of <SEP> Parts <SEP> component <SEP> of <SEP> Color <SEP> of <SEP> the
<tb>
 
 EMI18.2
 # ";: diazotization.: copulation.: dye on
 EMI18.3
 
<tb>: wool.
<tb>
<tb>



  35: 35.35 <SEP>: N-methyl-N-4'- <SEP>: <SEP> 42.2 <SEP>: N-ethyl-N-4'-sulfo-. <SEP>: Bluish red <SEP>
<tb>
 
 EMI18.4
 35 35.35: chloroacetylamino-: acid phenylamide =
 EMI18.5
 
<tb>: phenyl-amide <SEP> of <SEP>: of <SEP> 2-amino-8-hydro-
<tb>
<tb>
<tb>: the acid <SEP> 2-amino- <SEP>: xy-naphthalene- <SEP> 6-
<tb>
<tb>
<tb> benzene-1-sulfoni <SEP>: sulfonic.
<tb>
<tb>



  :than.
<tb>
 
 EMI18.6
 



  : 36: 42.3! 1N-methyl-N- [2 '- (4 "42.2: chlcrophenoxy) -5'-.
 EMI18.7
 
<tb> chloro-pheyl
<tb>: amide <SEP> of <SEP> acid
<tb>: 2-amino-benzene-1- <SEP>. <SEP>
<tb>: sulfonic.
<tb>
 
 EMI18.8
 s. . s -. - - -


    

Claims (1)

R E S U M E The present invention comprises noted: 1) A process for the preparation of mono-azo dyes, process according to which one copulates, in an acid medium, a EMI19.1 diazotized 2-arnino-benzene-1-sulfon-li oue compound bearing the sulfonyl'-que -53-R substituent, in which R represents a hydrocarbon or aryloxyl residue or an organic amine residue and in which all the organic residues can still bear other substituents, with a 2-amino-naphthalenesulfonamide coupling in position 1, the sulfonamide nitrogen of which can carry as a substituent an organic sulfenated residue and EMI19.2 the naphthalene nucleus of which optionally contains a jra., 1-- hydroxyl in position 8., 2) The embodiments of the process specified under 1 having the following features taken separately or in combination a) one uses identified component of copulation a EMI19.3 2-amino-naphthalene-sulfattiide, the sulfonamide nitrogen of which bears as substituents a sulfo-aryl residue and a lower alkyl residue and the naphthalene ring of which optionally contains a hydroxyl group in position 8; b) one uses as component of copulation a EMI19.4 2-amino-8-hy3re-napr.talene-6-sulfonamide which carries on the sulfonamide nitrogen atom as an alkyl residue and a sulfonated aryl residue, 3) As new industrial products: a) mono-azo dyes prepared by the process specified under 1 and 2 or by any other process; b) materials, in particular natural or synthetic polypeptide fibers, dyed with colo- EMI19.5 mono-azo rants c pi-f'iF 'Rnus 3 a)