DE1419873A1 - Process for the preparation of basic dyes - Google Patents

Description

Basel (Schwelg - SC ^ / Case 108ft / 1086 f \

Process for the production of basic dyes

Shaped structures, the essential component of which is polyacrylic " nitrile, as is well known, can only be colored using special processes or selected dyes, see above you can, for example, polyacrylonitrile with certain sulfonic acid group-containing dyes in the presence of copper (I) ions according to the so-called cupro-ion dyeing method in real, dyeing light to deep shades, the process is unfortunately a bit cumbersome. Disperse dyes deliver on acrylic fibers only light colors and only a comparatively narrow group of descendants from this class of dyes comes into question.

It has now been found that dyes which contain at least one ternary sulfur atom have ^{a good affinity for polyacrylonitrile fibers even at temperatures below 100 °} C. and are therefore very good for dyeing and printing formed structures made of polyacrylonitrile or of copolymers or materials that Contain polyacrylonitrile as an essential component, are suitable.

The subject of the present invention is · ^ = zwv

Production of new basic curbs'/> i,

009813/1203

A -r- R ₁ - S - R ₀
1 _f 2

wherein A is the remainder of one of coordinatively bonded

Metal atoms, carboxylic acid and sulfonic acid

groups of free dye, Rj one via a nitrogen atom with the remainder A

connected divalent organic radical, R _{2 is} an organic radical which is linked to the nitrogen atom connecting _{the radicals A and R 1}

can be,
R-, an optionally substituted alkyl or ■■

Aralkyl radical and
X ^ ZJ mean an anion equivalent to the dye cation.

The process for making the new basic dyes is that one has a sulfide of the formula

wherein A _{1 is} the radical of a dye or of a dye-free radical, free of coordinatively bonded metal atoms, carboxylic acid and sulfonic acid groups

ζ £ enabled connection,

* - R ₁ has a nitrogen atom with the remainder A ₁

^ linked divalent organic radical and

cn P. -inof; or · -2-mi. see ? ■■:; -.- :: t, the one with whom the leftovers

• θ ' A ₁ i \ ix (x R ₅ ^, erbinu' ■■ - ■? ■: - ,.: ^ ii S tickst off atom linked

- ■ u bsdeuten. BADONIGiNAL

141S873

reacting corresponding tertiary sulfonium salt and the reaction product obtained when A ₁ is the radical a compound capable of dye formation con - - with a Alkylierimgs- or aralkylating agent in the "stands j ^ transferred by appropriate reaction in a basic dye - .;"".

The production dör used as the starting material sulphides can be done d &duroh; that one eto amine of the formula

HUR ₁ -SR ₀

R,;

where R, and R «have the meanings mentioned at the beginning; * 'have ^ and R is hydrogen, a monovalent organic radical ΐ | or, together with R_, a divalent organic ^^

Rest means ». 1%

with at least one exchangeable halogen atom enfc ^.

holding dye, which does not have any coordinatively bound ^ ■ ^; Metal atoms, no carboxylic acid or sulfonic acid group anyway

holds, or such, be for dye formation

capable compound, optionally in the presence of a suitable one Buffer space and at elevated temperature, in an inert Solvent or in aqueous solution or suspension to- ',; ■■

c. puts. ν

The sulphides can also be produced in such a way that one Halogen compound of the formula

A, - R, - halogen

in which A ₁ and R _{1 have} the meanings mentioned at the outset, {in an inert solvent or in aqueous solution or suspension and in the presence of suitable alkaline condensing agents and at elevated temperature with a mercaptan of the formula 609813/1 * 6 »OBIGINAL INSPECTED

HSR ₂
wherein R _{2 has} the meaning mentioned at the beginning.

All dye values come into consideration, for example the anthrachinone, triphenylmeV, cyanine, styryl, perinone, Naphthoquinones, nitro, oxazine, thiazine, chlorophthalone, Azomethine or, in particular, the azo dye series. Leftovers of compounds capable of dyeing off are preferred those obtained by reacting with a diazonium salt can be converted into azo dyes, or compounds which have a dl & zotbaren amine group or one in such a Contain convertible substituents and which, if appropriate after conversion of the substituent into the free one Amino group diazotized and coupled with an azo component can be. Azole coupling becomes advantageous in a known manner in weakly alkaline to acidic, optionally buffered, medium.

The reaction of the sulfide with the alkylating or aralkylating agent to the tertiary sulfonium compound is preferably carried out in an inert solvent or optionally in aqueous suspension oiler without solvent in

- or . Aralkylating agent I

an excess of the alkyl residue liquid 4Hid at elevated temperatures

and in optionally buffered medium. «Suitable

Alkylating or aralkylating agents are, for example, the esters of strong mineral acids and organic sulfonic acids,
Alkyl chlorides, bromides and iodides, aralkyl halides, dial-

alkyl sulfates and, where appropriate, benzene sulfone

809813/1263

- # 1418873

acid esters such as dia Moi-hyi-, Aei; hyl-, propyl-, n-ButyX-ester benzene sulfonic acid, 2- or 4-methylbenzenesulfonic acid, 4-chlorobenzenesulfonic acid or ^ -nitrobenzenesulfonic acid. the The water-soluble dyes formed are separated off after one of the usual basic operations such as Piltratlon, evaporation and filtration, precipitation with a suitable medium and filtration.

Anlons X include both organic and inorganic ions to understand, for example the forraiat-, acetate · », Qxalat-, Lactate ions or the chloride, bromide, iodide, methyl sulfate, Aethylsulfat-, sulfate-, bisulfat-, BenEOleulfonat-, ^ -Methylbenzenesulfonat-, ^ -Chlorobenaor.sulfonat-Idnen. Also useful are water-soluble double alkali compounds of the »dye bases with certain inorganic salts such as zinc chloride.

If the anion-supplying compounds are used, if appropriate higher fat substituted by nonionogenic groups " acids such as caproic acid, oenanthic acid, caprylic acid, pelargon-8 & ure, Capric acid, undecylic acid, lauric acid, tridecylic acid, Myrlstic acid, fentadecyls & tare, palmitic acid, uric acid, Stearic acid, nondecylic acid or arachlic acid as well as the unsaturated higher fatty acids such as oleic acid, elaidic acid, erucaic acid, 3eranic acid, linoleic acid, linolenic acid and others aromatic or aliphatic «(carbonic or sulphonic acid or phosphotungstic acid, phosphotungsten flaolybdenum acid, sillcomolybdic acid, Sillcowungstic acid, various other anorganic

BATH ORIGINAL

809813/1263

· 6 - 1418873

see complex saturations or Hoppe '.. salts, as well as sulfonic acid or / and dyes containing carboxylic acid groups and free dyestuff acids of metal coraplex dyes, such as sulfonic and carboxylic acid group-free metal complexes, are obtained in water and partly in organic solvents more or less insoluble salts.

The new basic dyes are used to level dyeing and printing of materials made of polymers ago more than 80% acrylic * nitrll, for example, polyacrylonitrile, eg ¹¹ ChPlOn ¹¹ (elngetragene trademark), and Copclymeren 95 # acrylonitrile and 5% vinyl acetate or methyl acrylate or methyl methacrylate in strong tones, which are good light, wash, sweat, sub-load. Have pleated, bfigel, water, sea water and bleach fastness. The dyeing with the claimed dyes is advantageously carried out in an aqueous medium, it being advisable to work in a neutral or acid medium at boiling temperature. The dyeing can of course also be carried out in a closed vessel at elevated temperature and under pressure. With the standard dyes, mixed fabrics containing polyacrylonitrile fibers can also be dyed very well. Some of them are also suitable for dyeing polyacrylonitrile in bulk in shades which are fast to light, wash and perspiration. In part, those descendants that have good solubility in organic solvents are also used for coloring oeuvres, varnishes, plastic materials,

BATH ORIGINAL

809813/1263

Plastics and cellulose peacefatfaeern suitable in bulk. Descendants, which by luring the dye bases with Inorganic complex acids, complex organic acids or even with acidic dyes can be obtained and in organic Are insoluble in solvents, they are partly also suitable as pigment dyes. For example, they can be dyed with acetate artificial selde and polyacrylonitrile fibers in the Meuse yellow to green tones, which are very beautiful exhibit.

Furthermore, some of the new basic Far ^ S'saf.fe can be used for many other purposes are used, such as dyeing of tanned cotton, woi: .e, silk, regenex * i «rter cellulose, synthetic polyamide fibers and paper in the spring manufacturing stage. It has sloh shown that you can take advantage of it too

two
Mixtures of or more basic dyes are used.

In the following examples, parts C are 1/8 parts and by percentages, percentages by weight are to be understood as the temperatures are given in degrees Celsius and the melting points are uncorrected.

example 1

93 parts of Aethy! Mercaptan, $ 00 parts of ethyl alcohol? utd 2Oi? Parts 30 # caustic soda are introduced at o ^ö., #If-er good Fuhren is instilled to the resulting Natriwmäthylmercapt "iölieung a

BATH 809813/1263

1418873

those from 2Y6 parts represent the Ye * bond of the formula

and 500 parts of ethyl alcohol, the resulting clear solution is stirred under reflux until the reaction has ended, the precipitated potassium chloride is filtered off and the excess solvent is first distilled off in vacuo and then the reaction product. The new compound distills very uniformly at 104 ° C. 105 ° and 0.00 ¹ I ram. The elemental analysis agrees very well with the calculated values ( calc. C ₁₂ H ₁₉ SN: C 68.9 #, H 9.09 l ·, S 15.3 #, N 6 , 7 <f> Oef ^ C 68.60, H 8.9 #, S $ 15.6, N 6.7 # 5.

To convert the sulfide into the corresponding sulfonium compound, 1 mol of the sulfide is passed with 1 pint of diethyl sulfate at 50 ° for 2k hours. The siliconium compound obtained is a viscous oil and corresponds to the formula

^CH i2 -

CH ₃ 0Η _Λ

S - C ₂ H ₅
^C 2 ^H 5

CH.

I ₃ -CH ₂ -SO ₄ .

14 parts of l-amino-4-nitrobenzo :. are made in a mixture

30 5 <ig »r l
30 parts · hydrochloric acid and 200 parts of water using a

809813/1263

BATH ORIGINARY

Solution of 7 parts of sodium nitrate in 20 ropes ifageer diazotized as usual. The dialogue solution is replaced at 5 ^J with an ice-cold solution of 37 ropes of the above aaolcoiaponente in 300 hrs of water and 12 ropes of 30% salic acid The resulting red batch was mixed with a solution of 34 parts of zinochloride in 200 parts of water. The precipitated sinking chloride double salt was filtered off and washed acid-free with dilute sodium chloride solution and dried good yield in scarlet, level tones of good light, wash, perspiration, sublimation, pleating, ironing, water, sea water, smoke gas and bleaching fastness _t

This gives similar SuIfoniumfarbstoffe when in the representation of the azo component Diath.ylsu.lfat durolr dimethyl sulfate, _benzene} 2 "or 4-methyl-, 2- or 4-Ghlorbenzolsulfonsäuremethyl- -äthyl-, propyl or butyl ester , Methane, ethane or butanesulphonic acid methyl or ethyl ester, methyl, ethyl, propyl or eutyl chloride, bromide or iodide, as long as it replaces bensyl chloride or bromide, one ends up gaseous or low-boiling alkyl! halogenide5 as methylene chloride, ethyl chloride, methyl bromide or Aethylbroaid _s so the alkylation is preferably performs in a DruckgeSss.

The coating of polyacrylonitrile fibers can be done S ₄ B ₁ as follows;

The obtainable by the above example Warbst & £ ': ί v / is ^, gege ~ appropriate in the presence of an m ohtionogenen or: _ vsionaktiven dispersants, with a little cold ¥ asssr Terpastet. One übergiei2t the paste with soft water r: m 60 * ₃ ^J stirring the resultant solution thoroughly to UIID it sets h.ernaöli to the Pärbebad. With the pre-cleaned "Orion 42 ⁿ (ice-bearing trademark) one goes at 40-50 ° in dp.:=» with 2% Essisn ^ nrCi 5 '£ sodium acetate and 5?> Iiatrium sulphate on the Greivlolri; a ^f is based on the material to be dyed, buffered dye bath uin, warms üIsbbs l ~ -ü ^ sani and colors for 1 hour at ICO '"'«

BATH ORIGINAL

8 0 9 8 1 3 ^; 1-ij

-

141 &87;

«» 5 CO CN

CO

CO cn ο OO

The colorations obtained were spt.lt, obtained anachlisally rinsed and dried again.

Other valuable basic azo dyes, which after the Details of Example 1 can be prepared described in the following table; they correspond to the

formula

^Λ Ά ^M - ¹ ^

Anion

^; 6th

example
No.

Hue di Colorations

4-nitrophenyl

do.

dc,

do.

> do* \ do, 3 do, 3 ic. - do.

j do.

j do.

1 H.

I H

δ'-cyano j do, jätnyl j

1 methyl j.Mssh?

do,

do

i -

j do

CH,

ORIGINAL BATHROOM

acharlacl

a char Iac!

sharp lacl:

saharlacfc scarlet fever Scarlet fever

acharlach

Red

acharlach 3charlach

play
p.

^Λ *

do.

do.

4 · nitrophenyl

4-chlorophenyl
4 -! - cyianophenyl

4-MethyX sulphonyl phenyl

^ -Dimethylamittosulfonyl phenyl

4-methylinosulfonylphenyl

4-Trifluormethy! Phenyl ^ -nitro-S-chlorophenyl 4-nitro-2-bromophenyl 4-nitro-a-cyanophenyl 2 ₁ 4-Dlnitrophenyl

4-nitro-S, 6-dichlorophenyl

2,4-dicyanophenyl Thiazolyl

Acetyl amino

Ethyl

do.

^V 6

Shade of the colorations outside Polyacrylnitx-1! Fibers *

[ H -CHj, - i _ do H U
I. H -CH ₂ -C do H 'CH ₂ - Aechyl do H CH ₂ -CH ₃ do. do H do. do H H do. do H do. do H do. do H do do H do. do H do do H do. do H do. do H do. do.

R,

CH ₂ -CH ₃

rct

acharlach

VQt

CH ^ red

orange orange orange

orange orange

orange

Red

Red

Red
bluish tint

Brown

Red
orange

809813/1263

example

s "■■ -

Benzothiazolyl
5-nitrate mazolyl
o-Nitrobenzothiazolyl 6-Mefchylsulfonylbanso

6-Dimefchyl amixiosizlf onjlbenzothiazolyl.

6-methjlaminosulfonyl benzothiazdlyl

6-methoxybenzothiazolyl "

6-methyibenzothiazolyl 5 »acetylthienyl
3-nitro-5 ~ acetylthienyl 2-chlorophenyl-

2-nitrophenyl

2, k, 6 ^: r-trinitrophenyl

2, iir-dichloropheny 1

4-acetylphenyl

do.
do.

do.

do.
do.

π "ί

H 'H.

H H

rl HHHHHHHH

Methyl methyl methyl

Methyl bromine

H H H H

H H H H H H H H H

Aefchyl

do.

ds.

do. ύο. ■

Ethyl

do. do. do. do. do. do. do. do. Ethyl

do.

methyl dc do. t Methc do do. xy H H

R,

do. do. do*

do. do.

do. do. do.

do, do.

Color shade color length Polyacrj trilfase

violet

Red

Red

Red Red

CH ₂ -CH ₃ -S -GSL = CiL

do. Scarlet fever do. violet do. blue do. galb do. yellow do. Red do. _> violet do. orange

scha:

OH ₃ OH ₃

Red

do. do ο

do.

do. do.

COPY

809813/1263

Bel- ..
game
Nrv ^R 4 X I. Ethyl ^H 6 Iarbton der
Colors a *
Ioiyacrylni
tril fiber ί C. Red ϊο. -CH ₂ -CH-S-CH ₂ -CH, do· MM
J CH ₂ -CH ₃ do. do· * * ϊ 4-acetylphenyl chlorine H do. 2
do. do'.. czi.
-CH ₂ -CH ₂ -S-CH ₂ -CH ₁ do 52 do.-. CP ₃ H do. do. do· do. bluestlchlg 53 4-acyl ~ 2rbromophenyl H H do. do. do;. do. do. 54 do. methyl H methyl do. do. do. - ^KC 4-NItS ¹ OS-ChI orpheny 1 H H Ethyl do. do. 56 do.. H H .Butyl do" do. 57 do. H ^% H do" do. Jiethyl do. 58 'do. methyl H Ethyl do 59 do. methyl H do. 60 do. Ethyl H methyl 61 4-nitro-2-cyanophenyl H H 33utyl 62 do. H H Ethyl 63 do. methyl H Butyl 64 do· do. H Propyl 65 do ^: Kethoxy CH,

β ρ i e 1 66

en amines of the formula

80 9813/1 2Θ-3

In the above table, as well as in the following tables and in the formulas 131 to I51, anion ^ 'stands for Cl ", Br", J ", HSO _1. ", H _o f0 _Ä ", 1/2 SOj," 7 ZnCl - ", CH-SO,",

* t c * r * r YYY

C ₂ H ₅ -SO ₅ -, C ₄ H ₉ -SO ₅ -, CH ₅ -O-SO ₅ ", C ₂ H ₅ -O-SO ₅ ",

CgHj.-SO, ", CFI ₅ -CgH ₄ -SO ₅ *" (ortho or para), Cl-CgH ₄ -SO. "(Ortho or para), NO ₂ -CgH ₄ -SO" (meta), HCOO ", CH, -COQ ~", C-Hc-COO ", C _x H ₁₇ -COO *", Cl-CH ₀ -CJO ", C ^ H ^ -COO", the lactate ^ oxalate, tartrate or CitratAon, the dyes being sufficiently water-soluble to be suitable for dyeing polyacrylonitrile fibers from aqueous solution. Anion ® can also contain the caproate, oenanthate, caprylate, pelargonate, caprate, undecylate, laurate, myristate, palmitate, stearate, arachinate, oleate, elaidlnate, eruoate, linoleate or Represent linolenatdon; In this case, the dyes are less soluble in water, but soluble in organic solvents, such as acetone, methylene chloride or dimethylformamide, and are suitable for: are used for dyeing cellulose-2 1/2 and 3-acetate and polyacrylonitrile in the Mass, as well as polyacrylonitrile from aqueous dispersion. Finally, anion ^ * can also mean a phosphotungstate, phosphotungstate, phoephorungstamolybdate, silicomolybdate or silicotungstate clay; in the process, dyes which are insoluble in water and in organic solvents are formed, which are valuable pigment dyes.

Example 66 .

22 parts of the tertiary amine of the formula

CH, - CH- ORIGINAL. WSFE

809813/1263 O " ^N ν

iff

- «» - 1418873

are dissolved in 50 parts of acetic acid. The clear solution thus obtained is added to a previously prepared diazole solution of 18 parts of 6-methoxy-2-am: Lnobenzothi £ izol, 250 parts of 100% sulfuric acid, 250 parts of water and 7 parts of sodium mitrite at 5 °. After coupling has ended, the reaction mixture is discharged onto 750 parts of ice and adjusted to pH 5 with about 500 parts of 30% sodium hydroxide solution with thorough stirring. The precipitated red dye is filtered off, washed neutral with dilute salt solution and dried. * The crude product, which is obtained in excellent yield *, is practically pure.
The ne; e dye corresponds to the formula:

H ₅ CO ^w * ^ X- /

The whole amount of what is obtained from the above Dye are in 1000 parts of Chlorber.sol and 200 ' Methyl alcohol dissolved at high temperature, with thorough stirring 40 parts of diethyl sulfate are added dropwise to the clear red solution, whereby the color of the solution changes to blue very quickly «

The double alkylation is complete after a short time. The reaction mass is allowed to cool, and the one formed is filtered Precipitation, washes it off and dries it.

The crude product obtained in excellent yield is practically pure and dissolves in water with magnificent brilliant blue color and in concentrated sulfuric acid with yellow color. The dye obtained dyes polyacrylate fibers in brilliant blue tones of excellent light, Washing, SohwelsB, Subliroier-, Plissier-, ironing, water, Sea water, smoke gas and bleach fastness and reserves the

BATH ORIGINAL

809813/1263

if necessary with FCA dealt! Wool * The dyeings obtained are also colored very unimportantly and are capable of equalizing The coloration of the constitution-similar color from the same diazo component and dläthylamlnobenzene as the coupling component is clearly superior.

The new dye according to the invention has the formula

S-

/ -ν

The coloring of polyacrylonitrile can never follow the example happen:

but deal LgMp *** ^ **** »dead * *

1 part of the above example is dissolved in 5000 parts of room temperature water * 100 parts of pre-cleaned polyacrylonitrile fabric are placed in the dye liquor acidified with 4% sulfuric acid at 50 °, the temperature is increased in the course of half an hour until boiling and stains for 1 hour at high temperature. Then it is rinsed and soaped at the boil for 20 minutes in a bath that contains 1 g / l of a non-toxic detergent. You rinse and dry.

Other valuable basic dyes, which can be prepared according to the information in Example 66, are in the described in the following table; they correspond to "3or form"!

-N-N

Anion

809813/1263

R ₇ 8th 0! X
mm ü H \ 63 < * R ₉ 1419873 Shade d «
Colorations
on poly-
acriln'i-
trilfiber at
game
No. N-methylbenzothiazolyl-2- H Σ H Ethyl blue 67 N-ethylbenzothiazolyl-2 » H H H do. do. Γ do. 68 N-Benzylbenzothi azolyl-2- H H H do. do. do. 69 N-Methy t-6 ~ methoxybenzo-
thiazolyiir2- H H H methyl dc. do. 70 do. H H H Propyl do. do. T do" H H / 12 Buiyl do. do. 72 do,
dd. H H 2 * -Cyan- "
ethyl do. do. 73 do* H H S * -Acetoxj
ethyl do. do* 7 * do. Me
thyl H Ethyl \ * do. 75 do. do. H do. do. do. 76 do. do. Me—
thyl do.
sr do. do. 77 do. Me-
thox; do. do. do. 78 do. Chlorine H do. do. do. 79 do. bromine do" do. do. 80 do. Aoe-
tyla
mino do" do. do" 81 N-methyl-6-methyl-oxybenzo-
thia «olyl-2- CP - * -CI ^ CB ^ -S- do. do. 32 do· H Ethyl blue » H do. -Ci ^ CH do. H 3813

4%

el - «Τ X H y do. Ed Hue of
Colorations
on poly-
acrilni-
tril fiber N-methyl-6 ~ ethoxybenzo ~
• ■ .thiaKolyl-2- H H EthyI Ί2 τ 2 J blue N-methyl-6-methylbenzo-
thiazolyl-2- H H do. do. do. N-Me thy lthi azoly1-2 - H H do. -CH ^ CHgS- violet N-ethylthiazolyl-2- H H do. do. do. N-methylpyridyl-2 H H do. do* red-violet N-methyl-ohinolyl-2- H H do. do. do. N-methyl-5-methyl-
thlazolyl-2- H H do. do. blue-violet N-methyltriazolyl-2- H H do· do. red-violet N-methylbenziraidazolyl 2 H H do. do. do. N-methyl-6-methyloxa-
zolyl-2- H H do. blue-violet N-methyl-6-raethoxyoxa-
solyl-2- H do. do.

809813/1263

Example 96

51 parts of the paraffin of the formula

OH 0 OH

O NH-

are in 5000 parts of chlorobenzene with 20 parts of dietary sulfate alkylated at 110 °. After the reaction has ended, which can be very easily followed from the precipitation of the reaction product, is filtered off cold and the suction filter with chlorobenzene well washed out. A blue powder is obtained, which .sioh in HgO dyes lustrous blue and polyacrylonitrile in bright blue tones. take place as follows: \

1 part of the dye obtainable according to the above example formula

HO 0 OH

O ₂ N 0 NH

I "Ί

CH-S-CH ₂ -CH,

is dissolved in 5000 parts of water at room temperature. 100 parts of Qam made of polyacrylonitrile staple fiber are initially added to the dye liquor acidified with 4% acetic acid

809813/1263

ao

50 ° inserted, followed by dyeing under pressure at 1>) ° for 1/2 hour. A blue-colored material with excellent fastness properties is obtained.

Rajua receives dyeings with similar fastness properties, if nan uses, for example, the following anthraquinone dyes:

0 R,

Anion

ia

809813/1263

example

2 σ

R,

809813/1263

I Amirsc I Gl

si

do dt »,

Methylamines

TiO

3r

4k #.

R,, and B., ZußÄißnser ?:

CH.-

-ZF,

Gto.

Amino

do.- -SH-Q.

OHi a

! H

j B'art) t; or "der

oiau

j Tue

fcig r

Example no.

I ₀

16

1T

Par bton of the colorations on polyacrylonitrile

OH

O CD CD

2 ^H 5 ^ -CH

C ₂ H ₅

NH

NO

OH

green Blue

30 parts of the dye obtained according to Example 9S; toi fes are dissolved with 5C parts of thiodiglycol and hot water. This solution is mixed with tragacanth diocyte 60: 10C0 to make 1000 parts of printable paste. The dcmit printed fabric Polyacrylonitrile is placed in the Sterndämifergidaitpft for 30 minutes. the Damping can also be irc boiler "at 0.5 atü öurehge? Ün:? T The lighteohtneity and dje ice smoothness of the full one thus attained blue print are very * good

Example 105

4-1 parts of the aldehyde cerium formula

W ₅ -S- (X ₂ CRz.

are with 300 parts of methyl alcohol, 7 parts of malononitrile and 0, lTei3eaPiperidin heated under reflux until the Condensation ends 1st. The course of condensation leaves very easily in optical * ways at the teeth of the

<and /
The deep yellow solution is cooled and the dyestuff which has precipitated out is filtered off. The new styryl dyestuff is obtained in very good yield. It dissolves in water with an old yellow color and gives polyacrylonitrile a very strong color level green tones of excellent light, washing, sweat, sublimation, pleating, ironing, water, sea water, smoke gas, carnonizing and bleaching fastness.

809813/1263

Polyacrylonitrile can be colored, for example, as follows:

1 part of the information given in the example below. available Dye of the formula

T- ■■ '.- ■ {{ · - ■■■ , V.

H ₅ CH ₂

GBkC-GN CN

is dissolved in 3000 parts of water at room temperature *, consisting of a blend fabric of 60% and 40% polyacrylonitrile Wol3.e, are placed 200 parts of material to be dyed in the acidic with sulfuric acid # 4 provided at 60 fleet ^0th One increases the temperature in the course of a: 1/2 hour to the boil and dye for another hour at high temperature. It is then rinsed and soaped for 20 minutes in a bath that contains 1 g / l of a nonionic detergent. After rinsing and drying, the result is a strong greenish yellow. colored> tissue ,, whose wool is reserved.

Dyeings with similar fastness properties are obtained if, for example, the following dyes are used:

* 21.

Anion w BAD ORIGINAL

809813/1263

Λ * ·

at
game
No. Methvl h ₉ -CH ₂ -CH "TLefchvl fJVAtt Hue of the coloring egg
on poly & oryl nitrile
fasting ^; 1θ6 Ethyl methyl
do. do. do. VJf <CV |> A
do. XW
107 Ethyl Ethyl do.. do. do. do. IO8 do. do. do. methyl do. do. 109 do* do. do Propyl do. do. 110 do. do. do. Butyl do. do. 111 do. do· do. Ethyl -COO-CH- do. η do. do. do. do. -COO-CpH ₅ do. 11? do" do. do. do. -JCOO-CgH ^ CN do. 114 do. do· do. do" -COO-CgH ^ Cl do. 115 do. do. do. do. -SO ₂ -CH ₃ do* 116 do. do. do. do. do. 117 do. do. do. do. do. 118 do. do* do. do. -SO ₂ -Q-Cl do. 119 do. do. do. do. do. IL j Cl do. / do. do. do. do. ~ ^B0 2 V / 121 do.

809813/1263

1418873

«! Play 122
5 parts of the dye of the formula

NC «

earthen with 10 parts of methyl alcohol, 20 Teiden diethyl sulfate and 1000 parts ilorbenzol at 8o ° heated to 4 ^ie alkylation terminated 1st. The reaction mixture is cooled and the dyestuff which has precipitated out is filtered off. The earthy, water-soluble nitrate dye dyes polyacrylonitrile in very even, pale shades of excellent light, wash, sweat, sublimation, pleated, hedgehog, water, sea water, smoke gas, carbonization and bleaching fastness. -s colors of polyacrylonitrile can be ZoB. done as follows:

Part of the dye of the formula obtainable according to the above information

H ₃ CH ₂ CO

CH ₂ -CH ₃

CH ₂ -CH ₂ - S -

CH ₂ -CH,

Approximately dissolved in 5000 parts of water at room temperature. 200 parts of the dyed material, consisting of a blend of 60 % polyacrylonitrile and ko% cotton,

(based on the weight of the material to be dyed) are placed in the liquor made with 4 % acetic acid and 5 % sodium sulphate-acid at 55 °. The dye is then dyed for 1/2 hour under pressure at 3 "-. fen receives a strong reddish yellow colored material whose .u "i" oj.xante ^v:; . 1 is reserved.

809813/1263

.36

Colorings with similar authenticity properties; nan, if for example, the following dyes are used:

HH

Anion

809813/1263

At-
s pie
No. CH ₂ -CH, do. Λ »« Ι / "» TI ν CH ₂ -CII, H Farotoa the
Colorations on
Pol jraoi'ylnifcril-
fa & arn 123 do. CH ₂ -CH ₃ H CHg-CIL H galb J24 do. -CHj. H geiu 325 do. - ^C 2% -CH, yellow 126 do. do. .-0-C ₂ H ₅ yellow do. -O-CH, yellow 128 do. H reddish yellow 129 " yellow -CH ₅ 150 yellow

also the dyes of the

/ hVnh

2 ^H 5

CO-NH-CHg-CH ₂ -S ^

CH ₂ -CH -CH.

809813/1263

greenish!

Anion

Anion * Zs onange

BAD üriiviw \ 'AL

HjC-H ₂ C

! -CS ₂ -CH ₂ -IIH-CO - ^ J HJ = N - <_ / " K ^

HjC

Anion orange

p. green tick anion yellow

L35

H/

136

CH,

CHg-CHj ¹ CH ₂ -CHj

Anion orange Anion pink

137

CH = CH

• v ^ ko-Cg ^

CHg-CHj

Cl

Anion

blue

Anion red

H, C-0

CHj Anion blue

S-CH ₂ -CH ₂ -O '

NH

/ CHj

^S0 2- \

CHj

Anion yellow

809813/1263

H _x C. NO ₂ 5

CH ₂ -GH,

/ CH ₉ -CH,

CH ₂ -

CH,

AnI on yellow

Θ ©

Yellow on Lon

H ₃ C-

H ₂

σ-QC

H(

CEL anion, yellow

Anion bluestiohlg red

0-CH ₃ OH -N = NC- (L.

-0 _Λ 3 '

Anion yellow

^H 5 ^C 2

S-CH ₀ -CH ₀ -N '^

f d. et \

^H 5 ^c a

C ₂ H ₅

Anion bl

, ^c a ^H 5

C ₂ H ₅ -S-CH ₂ -CO-

N = N

CH-

yellow

809813/1263 ORiGlMAL BATHROOM

COPY

14198

> H

CH,

Anion yellow

^0H

C ₂ H ₅ -S-CH ₂ -CH ₂ -Q-CO-HH- ^ VN = N

CH,

Anion

CH ₅ CH ₃ -S-CH ₂ -CH ₂ -O-CO-NH- / V- NN

CH,

Anion

Anion

gel

gel'

AL ^ SFECTEO

80981 3/1

Claims (8)

Patent claims: or together with R "a divalent organic R, a divalent organic radical and Rp mean a monovalent organic radical, with an alkylating or aralkylating agent in the associated tertiary sulfonium salt reacts and the obtained Reaction product, if A, for the remainder of a compound capable of dye formation, by suitable conversion converted into a basic dye. 2. The method according to claim 1, characterized in that that by carrying out the alkylation or aralkylation in an inert solvent and at elevated temperature ^v. 809813/1263 3 · The method according to claim 1, characterized in that that the alkylation or aralkylation is carried out in aqueous suspension. 4. The method according to claim 1, characterized in that the alkylation or aralkylation in buffered Medium performs. 5. The method according to claim 1, characterized in that the alkylation or aralkylation is carried out in the absence a solvent and in an excess of the alkylating agent or aralkylating agent. 6. The method according to claim 1, characterized in that to transfer the editorial products obtained, in which A, the remainder of one capable of dye formation Compound means, carries out an azo coupling in dyes. 7. The method according to claim 1, characterized in that to convert the reaction products obtained, in which A, the radical of a compound capable of dye formation, carries out a condensation in dyes. 8. The method according to claim 1, characterized in that that sulfonic acid and carboxylic acid group-free diazo compounds 809813/1263 fertilize with azo components of the formula 1419873 \ _ / \ / Alkyl / Alkylene-sC X ^N alkyl wherein X is hydrogen or methyl, couples. 9. The method according to claim 1, characterized in that that sulfonic acid and carboxylic acid group-free hydrazines with azo components of the formula Alkyl Vv ^N \ / ^alkyl / Alkylene-S ' X N where X is hydrogen or methyl, condenses. The patent attorney: 809813/1263