DE1444611A1 - Dye and its manufacturing process - Google Patents

Description

Orompton Je fnovles Corporation "* oreester" Massachusetts TJSA

dye and its production experience

The invention is based on its class of bonds » nemllch to dls Meta- and Fara-Bensoylohlorlde with the structural formula

(Structural form I)

and on the meta * and para-derate * of these bonds, the the Badikal]

T ^ (structural formula II)

or contain the radical!

G>

(Structural formula III)

(In these structural formulas, H means a -B or a lower alkyl radical.)

Bio XRF Indang inspects eioh further directed to a Herstsllungsrerfahren ά · τ Terbindungen having the structural formula I and their entepreohenden Derirate with the radicals according to the structure of formula II oderlll.

The bonds with the structural formula I kttanen from the ent spreohendon meta- or para-substituted. Intermediate products » the 2-hydroxyalkyl-sulfonylbic acid or the 2-chloroalkylsulfonylbic acid getting produced. These Iisisohenprodukte only need to be treated with reagents which contain the carbon convert acid group into an Oarbonvlohlöridgruppe, so that dls

Compounds of structural formula I are formed. Door this Purpose paseende * chlorinating reagents are thionyl chloride, Phos «-« phorpesitachlorid and the like. In these reagents can also at the same time any alkyl hydroxyl group present can be converted into the chloro group »If the alkyl chloro group is already present, it will of course not be affected by these reagents.

The intermediates 2-hydroxyalkylsulfonyl- or 2-chloroalkylsulfonylbenzoic acid are known compounds and can be produced in various ways. For the sake of simplicity however, the preparation of the intermediates is fairly, generally described; the explanation is limited to those cases where R in structural formula I is -R. Throughout the Description can also be lower alkyl; the compounds in which R differs from -H can thereby be prepared that ethylene chlorohydrin or ethylene oxide are used in the formation of the hydroxyalkylsulfonylhensoic acids, duroh a corresponding chlorine alcohol, «. B «2-chloropropanol, or by suitable Epozy compounds, s »3. propylene oxide; 1,2-butylene oxide etc. is replaced · Two possibilities for producing the intermediate products are now explained:

A) Reduction of a suitable (5- or 4-) chlorine ο sulfony! Benzoic acid to the corresponding sulfinic acid with the help of sodium sulfite or of zinc and an acid; Reaction of the sodium sulfinate with ethylene oxide or Xthylenohlorhydrin In alkaline ISsuag sum Manufacture of 2-? Hydroxyäthyleulfonj (benzoic acid

B) Condensation of 3- or 4-meroaptobenzoic acid with ethylene » chlorohydrin or ethylene oxide, followed by oxidation of 2-hydroxyethyl mercaptobenzoic acid (ζ · Β · with sodium hypochlorite or hydrogen peroxide) to 2 * hydroxyethylsulfonylbenzoic acid follows.

In diesen'beiden method, the aliphatic 'hydroxyl group can be replaced ansohlieSend duroh chloride ₉ by the product is treated at elevated temperature with concentrated hydrochloric acid. "

909822/1232

BATH

Me preparation of the compounds ait of the structural formula I ans These intermediates will be explained in detail later.

From the compounds of the formula Ϊ, the derivatives with of the structural formula II and HX are produced in the "eisten First of all, a derivative with the structural formula II is prepared, from which the derivative of the structural formula III is then produced.

Me derivatives of structural formula II are derived from the compounds old of the structural formula I daduroh produced "that these Yerbindungen a material that contains a functional group is reacted under its hydrogen atom the same conditions can be replaced »how the aroylohlor in connection with the structural formula I is activated and displaced» thus a functional group that produces the chlorine of a carbonyl chloride.

Bas β-chlorine and the aroyl chlorine of structural formula I have-one different · responsiveness, since the aroylohlor is more reactive than the / £ -chlorine 1st · If the formation of a derivative with the structural formula H should be guaranteed »without seeing at the same time a considerable amount of the derivative with the structural formula III forms “reaction conditions must be selected” in which the aroyl chlorine of the structural formula I is activated and “olme dafi” is displaced at the same time as the jS -chlorine will.

If the functional group of the material "that is to be combined with the structural formula 1 to form a derivative. With the structural formula II to react" is an amino "group", the reaction can in most cases without a significant displacement of the β - Chlorine are carried out »if the pH of the reaction mass is kept at about or below 7« Me choice of functional group »the temperature of the Eeaktionammese and the molar ratios of the 'reacting substances kStanen also affect the type of products formed · When the attachment of the Amino group and its activation

909822/1232 ^BAD oriq _{! Nal}

tion Re @ ätioas ^ edingUBg «^ requires« you something more favorable for the

β- chlorine are provided for in all cases.

that the molar Eonsentration of the compound having the structural formula I to the molar Koßsentration gleioh the material "road or this About et" IGT, dee the * for forming derivative nlt the structural formula ΣΧ mat reaction gebraoht is ι examined thereby newly siohersuetellcn the vorsugirweise displacement of Aroylohlors .

The derivatives with structural formula III are usually prepared from the derivatives with structural formula II; a connection can make some * βά jedoch- ^ on the Strükturforoel I ausgeSieUt% m the derivative having the structural formula lit in a einasigen operation received au without DAFL el oh an intermediate i form & Φ "derivative forms having the structural formula II '

The derivatives with the structural formula lit are made from the intermediates with the structural formula II formed by "that a sol * ones intermediate product with one. Material brought to the reaction what contains a functional group becomes its water atom can be produced under the same conditions as dasyS -chlorine of the derivative with structural formula II activated and displaced can be; the functional group of the material "must therefore be able to react with the chloroalkyleulfonyl group"

If the fractional group associated with the material structural formula II stubborn reaction should be gehraont an amino group So B-. a -ϊΐΗ ^ -βΓύρρβ, the reaction in the acid otter can be alkaline State expire «Bs must, however, be avoided that the reaction under initially strong alkaline or extremely acidic Conditions expires, since then a tydrolysis of the amide link knows the actual conditions applied for the pB value sl & d by the stability of the reacting with one another Substances and the reaction products specified

When the functional group of the material associated with the intermediate or the derivative of structural formula II is to react, sine is hydroxyl group, the reaction can take precautionary measures

909822 / .1232

BAD OR

U44611

alkaline conditions, eg run in the presence of strong bases, sodium hydroxide, trisodium phosphate and the like and can be used as a slarebinder for the production of the natural type of beaondera. In most cases, the standard should be comparable to that of the sodium hydroxide solution obtained, which has a weight of about 1/2 - 4. In the case of many materials which contain an -OH group of ale functional group, the reaction proceeds easily at room temperature; in some cases, however, one aöohtt the reaction by heating sometimes up insehleuiiigen to a temperature of 100 ⁰ C »The upper Temperaturgrense is jedooh eo long as the reactants and reaction products can not withstand these temperatures spesiellen critical» »

You most natural and synthetic Textilfaaern contain long-chain polymers that fractional to versohiedenen points of the chain groups, B. · s »IB, NH ₂ and have * 0H: · The cellulose derivatives" such as cotton and ₀ ^ TlskosefEse are typical textile fiber »With hydroxyl groups as functional groups. They are only adversely affected to an insignificant extent if they are treated under alkaline conditions, under which the β «» chlorine of the derivatives with the structural formula. II is displaced · Wool, silk and ion are typical textile fibers with functional amino groups; these fibers (be the manohmal also beseiohnet as polyamide fibers) are neutral or be * voted acidic conditions slenlieh stable "the sur YerdrKngung of ρ" chloride can be turned into the derivatives having the structural formula II ""

Therefore, the compounds with the structural formula I are used as reagents usable »which adhere permanently to the textile fibers ι these ktenen with the compounds of the structural formula I sur reaction gebraohV are »so that the derivatives of structural formula II result.

Numerous well-known textile additives contain something unfamiliar Points of their structural formula amino groups) solohe functional

909822/1232

BATH ORIGINAL

H4461

eewBfaaliQh also ta> @ l2 © te © ntspreobenfles r »n be introduced. ? 1 «1«! Msaißetofäft react to «i © ii nlt ¥ «s £ & lfaeem» Thus Si «are connections with the nel 1 at β «? Manufacture Ten feztilOTgatssioffen, the »it dsm

ssur 3 $ elg $ r * axgg der

_t if £! ©. * & only slightly

; B8B © i »ha"<^, f ²ⁱ 2öS; til «ueiit« steff ^w ii © runs on Färleia mä iipp ^ eti ©! »« «. Vca f # stiliea (s · Bc atif

t @ rii3a _f mcr Te ^ & dltmig edtess Sleitena, mimg ¹ UHi sim ieteti Gegesi @M TerMasioE aia dar Atmoepäiär «* on Batwi @ kler _g Oiasoliaeent larteteffiswlsehesprodukte»

Weiohaaoh? & ^ it-fcisXr waese ^ sl ^ it @ i®ndi © Iif1; t2 _c opt-ί see, and spesiell®? nrb @ t @ ffe all «r

If aim 9 @% til £ usatset @ ff aiii

mel 1 be * R «akti @ ag®% ra @ lit wii> i _e we3? i <»? @ i * eelii @ S «you meet

where JS contains the meta * and

* "0—> A ütl © r« * C

means·

(In this structural formula / oedfff t * ■ - &
via a functional group angtäüft® ¹

stoffatoa Teraringt- ist «, 3ani -B i £ mi @ gt _ß ter tob. the ■■; ■■ '909322/1233'^'-:;

_BATH

• at «let formed after condensation» it is Garbonylohlorid • Form in a heterogeneous system

t7sBtt eia Derirat der Strukturforael 12 τοη der special form should be sucked

/ \ -O) ₂ -ORH-OR ₂ -Ol (structural formula IIa-1) 0-0

The connection with the structural formula I is brewed as a reaction with a textile additive that has a functional group, s · B · -KHg. or -VH- at the desired attachment point. In general, the reaction takes place under approximately neutral conditions · to support the course of the reaction, acid-binding agents »see, for example, sodium bicarbonate, fatrium acetate or lithium carbonate can be used« if, however, the reaction product old Substsase or materials that have functional groups «may undergo another reaction» the β- chlorine of the Ohloroalkyleulfons not be replaced; therefore the pH should be kept approximately neutral during the reaction.

fena derivatives old of the structural formula Ha are to be produced » la deneäs

enteprleht »the connection old the structural forael 2 old one Terbinduac aar condensate loa brewed, their two functional Dre eo Hegen »that formed a heterosycllsohss Rincsystsa will] aa these pillars s. B «the orthoaromatic Dlanine and other ihalle polyfunctional compounds, which are sua at least elae contain laino group and condensable under neutral conditions are, so that a heterosyclieohee ring system arises.

909822/1232 bad original

H4461T

Vs ί, ί

\ icS31

Ü
&

_r ^ tt. ιπΜιΙίιι Hi iff eRiftmflMiSbritoAArffSbg ^, ^ MA ^ efi * ι iiaM Λ ι ι! Ulli ■ flitl ^: ^ A ^^^ W ^^ Mk WA ^ ^ - -

other Ae * »it der SStrufetovfozs ·! m. received

fStnaktiirfprael XXX b)

i.

(A · mi A "represent a number of different dyes, which are above This fnaktioaelie group are not affiliated, except for a Waaaerateffato * Terdrlaft 1st ·). On the white canoe, see e.g. a blue dye alt · * & ·· g «lben dye are concatenated« eo that eioh a green dye gives

909822/1232

BAD 0RIQI ^ 4AL

~ 9-

01 · ΤμΜβοββιβ * Bit of the structural form «l X slaa lasbe * oiid« r · Beretellea ¥ · ■ TextllsueatMtoffea Bit tor Stformel IZ brewable, dl · a · lamk old Yereohiedemen fibrous materials are made reactive, dl · Ib their processing · Or contain reactive yoacy »odor amino groups; maoh a eoleh reaction M UUtB β · Γ D «rtT» t · with OM Strekturfonwl III and dU «U« dchain β · β «Mbarf · Wa« 4) «ltt« l sod -b «dla« une * n etaMl « · Ο dal dam lM «vst« ff «B τ! · 1 · latent wrwtaecht ·, dautrhtft ·

Si · nleaUgrlaa t «rtilaueataetoff · alad biar Al« frttetoff ·· Iaeh i «ar ReaktlCMi odar naoh a ·« laheft · »aa di · ftxtlXTMern ^ aeltiam dl · · τίΐΒ« «Μ {·« ηΜ b «r« ittt « a Tftrtotoff "tin" flM * bmuulll & * i% |

VBi · 1 »·» MAfeetlikelt, dl · a «oh Bit Ib übliohw W ·! ·· aufftfermeh-

t «B Parb ^ offan erhlltUoh 1st. VI · ready · warmed up, ketones dl · TaafelttdvBgaB old dar structure? «« ·! I can be attached to Sueataatoffen via a fwüttlonell · group «dl · daa Ohlor of a carbonyl« obloridcrupp · erpetaen) The wlohtlceten groups are dl · Aelnoe -WBj uad «4ΠΕ- · Anlnoemppen« ldreiohen lowerohledllehea dyes . la.Aso-t inthraohlnon-, baaleohefl, Dlpheny: "rtnan-, Vapkthalocyanin-, Trlpfaenylaethan", Iltro- WtA Hitrodipkenylavlnfarbetof f en TorbaBdaa or -kauen. Ib dl ·· be introduced · ...

Inder · Textllawatsatoffe («X · colorants) ktenen aaeh Bit den Oarbonjlahlorld ^ rttppea der Terbjndungen goBVJ der ErflndUBf umter ( ltthllfineheie τοη amino groups (or other, in thr« i Amfb · »rorhimdener groups), so condensed Befeetifungemögliohkelt Bit help dea ahloroKthyleulfOewl-alale on laeem or other materials, whose functional groups bit an Ohloroalkyleulfonyl Reaglerett and

JfJ daa Ohlor YMrdrttngen

«Ο _β _.

fodie Brauo |! ib "of Terbindungen rkelt old structural formula I ala ^ aktlTiereade and rerkettende Beagenslen 1st nioht" Bf 1 extlllea j ^ beeohrtmkti · kttomen AUOH ear training tob Brüoken Or aiiedern ω (structural formula II) mix rertrmgliohen materials inwendung FIM ¹ ^ those which contain functional groups of the kind already mentioned.

BATH ORIGINAL

The following examples explain how to establish a connection and derivative gen * dtr charge in the examples are di Partial Oewichtsantelle «ad dl Prosente als eewiolxteprosente ansaeehea, and dl ffeaperatur lat la Grad Gelsiu specified.

Production of 4- ^ -OaorotthylsulfonylJ-beiiBoylehlorid. 154 * 2 feil · 4-Xereaptobensoeattur · throw at 35 ° la 1500 fells of water dissolved, since it contains 100 parts of sodium hydroxide and 30 parts long drop white old 85 files treated with ethylene chloride Kaoh an additional 15 minutes of stirring, concentrated hydrochloric acid is turned off pR-Wtrt of 1.5 Mnsugeeetiti der nahesu Quantitative * colorless Iledwrsahlsg of 4- (2- ^ ydroxyIthylaero »pto) -benaoic acid is filtered, washed old cold water and dried · the raw · » a material sohailst at 146 - 148 ° ι by recrystallization the water point rises to 151 ♦ 153 °. .

198.2 inexpensive 4 * (2-Qrdroacyäthylaeroapto) -bensoeeäure la resolve 1ooo skins water 4C bargain · latriuahydrozid entailt · At 20 °, 1200 fell · commercial latriuahypochloritloauag (-12.4 <VaOOl) dropwise 2 indeed long. The solution is heated to 45 ° for 1 hour and then to 70 ° for a further 45 ° until the presence of the father's hypochlorite from iodine starch paper cannot be reduced. The solution is cooled outside to 20.degree. C. then salsic acid is added to pH 1.5 and the colorless, crystalline mixture of 4- (2-iydrojtylthyleulfonyl) benzoic acid is filtered. Freed from water and gives 1 (3 feil. (71 4 of the theoretical yield) "the line recrystallization from 95% ethanol gives 100 feil" Rohawtorlal, the bsi 193-194 ^o eoiaul "t.

93 files of pure 4- (2-Hydroxyäthyletilfonyl) -gleichee acid and 0.5 skins fyridlfi got old 180. skins hoohgradlgen fhionylohloride at 30 ° 10 BLB long treated langssB, heated to 90 °; it becomes sueret goose viscous * but forms eohlieSHoh a clear solution. ! Taoh another 1.5 h Srwäraans

90.9822 / 1232 "

toi 90 ° "1st the wets *" when 75 ° cooled down! 100 fur · Bsnsol «• vita nlBsagsfUgt, * b * Al · BaBsel-moBjfchlorldrttlaohBttg will in a fvff tol of a temperature of up to 99 ° Another part of 100 great «BtBBOl will be a bit of a fopfteape · ntc »tob 13θΡ la Italian catfish sbdeetiliiert, se da * 11 $ Toil · 01 s «rttekblolben · BMIi des AbWkUa r« rftctift »loh Am ÖL BU OiBBB loioM goftrfcton footkOrpor «der b« l 95 - 9T ° oo! »Llrt. BiBO BoltrietBllioBtioB aas dos BobboI leads iu oiBoa foxbloacn, krietBlliBOB product that offered 9 € - 97 ° sehailBt md al 4- (2-

bonBogrlohlorid identified 1st.

Boianiol t

from 5- (2- <niJapolthjrliulfonyl) -benBoylohlorl (J ·. * Bot of TtMBBdVBg tob 3 <4loroaptoboBBoeeB] ir · (prepares ana a la Bendel.Torf0 «bexen B-ABinobenaooaittre) anetelle of the 4-4Kerereeaptare do 4 1 results in the corresponding 3 "(2-HydrocytB7lBeroapto) -bensot" ttur ·· Bas at 70 - 75 ° 90 - 91 *.

196 «2 part · 5- (2- ^ dro« ^ äthyln «roapto) -btn» oeeattre «earth dissolved in 1000 parts of water, which contains 40 foils of latriunhjdroxid, BBd as in example 1 with 1200 skins of commercially available VatrttahTpoehlorldlOetmg oxidized, so that see * 5 * (2 ^ ydroxy-Athy 1 sulfonyl) -bensoeeaiire forms · Bas crude product from d Wasssr rskrlstalUelert · wherein fled 166 feile a colorless "at 160-164 ° sohBelsondsn Vateriale yield. A recalculation from 99 <igeei Ithanol results in 138 layers of a soBBolBS & dsB product at 167 -168 °

161 foils of pure 3 - (2-5% roxyethyleulfonyl) -beasoetaure, 0.5 Feile rjridln and 350 Feile high-grade thione / chloride rerwieoht and heated to 90 ° for 2.5 hours. You see submissive Reading is wi * Ib Example 1 through Susats and distillation several parts of anhydrous Bensol τοη ttbersohUssigsB Thionyl « ohlorid freed * The oily back tend to be 190 parts

9098 ^ 2 / 123'2

BATHROOM CTUGINAL

Abfcfänlem the product becomes crystalline

and utitt 'eiSiA Ssi »lsp! s» kt 7OB 55 * 37 ° to · 5 «let in Löeeeit-. ₉ 3 »g © l heS Aeefonj eenr leicht leslie» and «3. · 3- (2-

^ lAeatifistert · ·

12 S @ ile 7ο ^ ώ3β »1 ^ β $ 1ϋ & ιβ ^ 5Μηι14αΒΒβν * · value how? Bezratstmg 5 ffsiles Vfttrlusäatfbottmt in '100' ffeilen Waes «r ait tin ·« pE-

@ feil

al® Y & rhiMmß nit Aev

etoift ^) §% ttea ^ f wesHlea® leia Herrteile fabrics ksnn isle -in lieung euen els. ! © wlmmgeembetane application. find · Me.-tffbtadung can isolate their outlet »getreeknet, and aneenlie ^ tnd them Kopplusgeeubetans or Sntwiokle? pitted will"

Example 4 .

Bine £ ββ * η $ sue 1 feil dee product «! According to Example 3, in 50 files of 2S ° is used as a Rtüokes spun co Kuttstseidengewebee · Lake fabric is rolled and then "with a 'S XOeung tone 1" Hatriuahydscid and 30 <sodium chloride "soaked in water ^. The tissue is for 5 min at 105 ° dried well in ^ taeser and then in a £ öeung From 1 ^ lTatriunbikarbonät in - * abgeepült water and cleaned at the boiling point in water containing 0.1 f contains a non-ionic '.Vaaohaittele ( eB · Triton 1-100, ^ sin nichtionieohee, surface actiree means of Uama Röha A Baas Oonp ·) · Bas tissue is rinsed and dried and possessed

■ · · -BAD

4am · 1λ · etrobbltlohe for »4, the la alkuliaefcer Itfewag la OeIb uaeehlagt »2> ae tissue is la three * tUake aeraefcalttea wad nater Xueat «of the following three Dieeoniuaealiloeungen la kalter, 5 ftftr latriuakarboaatlBettng developed # «o dafl eioh« ear waeoheohto colors eraebeai

Masonluaealaltamg der ! Arte Ketealleftnre aoaarlaoa

4-Ketaoaqraet «ill« iare red

9 * AalBO-6 ^ Mthoxynmpb'thalin-2- «ulfon« aur «violet

24 fell · the 7-Aaino-1-a »phthol-3-eulfonBättr ·, dissolved at 50 ° la 200 files V «eeer old 6 parts a catrite carbonate old 16 file Hatriuablkiurboafet and then with vigorous stirring old of a LSanae ane 28 parts of 3 ~ (2-OhiroEthyleulfonyl) -ben «oyloalorid handled in 40 files aoeton. Xaoa 9 aia becomes the eiea resulting loeeaf old cooled down to 15 °, and 20 feiU letriüabikarboaat will be BiaaugeitSgt. laiwioohen will be neutral LDetmg of 21 files 4-MethoatyaetaaileH.ure old 2 $ files more concentrated SalaeMure aagtiliaert and at 0 ° old a shade of 7 for sale filing latriaanitrlt la 25 parts Waeeer dlaaotiert · Dieee Dia- ■ oaluaealallfeuag long a water good stirring at 10 ° the EopplerlOetmg alt eiaea pH value tone 7 »0 - 7» 5 ainsttgeeest · laoa For 1 hour, the pR value is reduced to 5.0 with 20 parts of Beeige & ure 800 files Löenag are treated with 80 parts Batriuaohlorld The red larbetoff which has precipitated out is filtered uad la Takuua dried, whereby eloa 83 parts result in it let ait Oelluloee · Feel able to react and change the structural formula

909822/1232 ^{BAD OftiQINAL}

U44611

fenm 21 Ml i-Kethoxymetaniliiäuin i Example 5 through 18 Partly Metanilsfture will be an awer, reactive ·? dye »obtained from the following structural elements, the jBelluloeefaaem «oharlfteh colors w & i a · atiagestiolmett

wa, Ü «in · good · Idolit # dlith« it aufirtieti

Ι · ί · Ρΐ · 1 f

Solution from 1S ₉ p

in SOO T «ilen Ύ & βββΓ w ± tü at 4 @ ° leads strongly ^. rad sit • in ·? I (ößu? I £ e & @. ?? ^ eilsn 4 «? C ^" 3M®roätl! YXevLlf <> nyl} «b« LBoyl · »ohlorid Ic 100 parts aoeton ΙκιΙίΐιιιβ®! ^ ® la« »doi Ab ^v BbJil «£ the Beafclion is the pB» W «Tt.iBit Bsei ^ cäur® reduced to 5 md the ferbloce, crystalline« Predakt pit d «r structural form is filtered!

This color-like product can be applied to * di · fibrous · material or used as a wiping product, so that biases and xepplution reactions can be converted into reactive dyestuff · vuag ·.

Example 8

Idea for 1 feil de products based on Example 7 in 50 parts Water is spun onto an artificial silk fabric at 25 ° eaten up. Sa · fabric is dried with a solution τοη

909822/1232

ORIGINAL

Drank latrium hydroxide and 50 $ sodium chloride in water, dried the oven at 105 °, rinsed in water and thinly in 1 liter of sodium carbonate solution, and cleaned it at the boiling point in water The tissue is placed in an ice-cold bath with ohtieisser nitrous acid, where it remains for 10 minutes , which contain excess amounts of water-soluble developers · The following table shows the developers and the colors achieved with them, which are very fast and rewarding

Developer color

Barbituric acid yellow 3-Kethyl »1- (p-sulfophenyi) ~ 2-pyrazole ~ 5-1 yellow

Resorcinol orange

3-Hydroxy-2-niiphthanilide red

6-Amino-1-naphthol-3-eulf'onic acid soharläch

8-Amino-1-naphthol-3,6 »disulfonic acid chestnut brown

Example 9

9.4 parts of a neutral LÖeung of 2,5-Diamlnobenzoleulfoz acid in 100 parts of water at 4O ^- under vigorous stirring with a solution of 14 parts of 3- (2-Chloroäthylsulfonyl> beneoylchloride in 25 parts of acetone treated "If the mehrbasieohe 5 -Aoino group is completely acylated, the pH of the solution is lowered to 5 with acetic acid and the product is separated off. At / 0 °, it is diazotized with a solution of 3.5 parts of sodium nitrite in the presence of excess hydrochloric acid Siasoniumsalzes su a neutral solution of 12.7 parts of 3-Kethyl-1- (4-sulfophenyl) -2-pyrazole-5-1 in 250 parts of water containing 15 parts of sodium bicarbonate gives a yellow solution, i_us by adding 125 parts of sodium chloride will separate a dye with the formula i

909822/1232

BATH ORIGINAL

< - 4S I © ΓΙ?

; -O ¹

⁷ E-

1- - η -

iooc lc air

_ C IL:. "O *

scig ^

© folio 5 ^? ^ ^Ι οί? @ == 4 "= '©

as

iMe

foiled

g rope

S ?, Aa © e,? A @ sa sit

In 4Ö & ropes

ai'fe

resolved ι this »On what

2/1232

ORIGINAL·

• In · Solution 28 parts of 4- (2-τοη Ohloroäth rl3uli ^ ¹ o »Ti; -5 © nasoylohlorid In 100 part ·» acetone is hlnsageaetst Ss falls from a "rötliobgelbe Uasse, the filtered» once with 90 ropes Nasser washed. Viscose fibers are introduced into a solution of the product in water at 80 °, dried, treated with a reading of tf> HaOH and 30 # NaCl, dried at 109 ° and washed in water, the sia nloiitioßieohee detergent ( Sriton 1-100) contains} the dried fibers «own then, a lloht- and washfast, orange-yellow-yellow shade.

Example 12

71.4- cases of a solution from the connection with the structural formula *

(prepares a condensation of 1-amino-4-bromo-anthraphinone-2-eulfona acid with 4 _v 4 ¹ -I) laminoblphenyl-2 _t 2 ^t -41eu | phonopic acid in 600 parts of water and 20 parts of sodium bicarbonate dsm pfcYert 7 »5 are treated at 50 ° with a solution of 28 parts of M2.-Chlproäthyleulfonyl) -benaoylchloricl. After 30 minutes the pH is lowered to 5.0 with acetic acid; the product is isolated by jellyfish and dried in vacuo. It is a blue, synthetic substance, reactive and produces blue, lightfast and washable dyes.

Example 13

77 _f 1 parts of the connection .. old the formula * V - V - / Voa - CH-Λ. V HH ₂

(prepared using the process described in V3 patent specification 2,795,577 "Boisplel 6") in 1,600 parts of water and 28 parts of Hatrltu

-909822/1232

BATH ORIGINAL

10 '

te 100 ropes AoQtQ & 'at 50 * .oeäelte »flfegfc 30 Bin will e filtered 5 mafi®s worth 3i® wedge «latriuffioaiorld ito ba? Crystalline üiei ^ raslslag like® aerobic * Filtrierenls # « ia # in the fskwm getrea & aste Bas Sroäukt --stigt tu iHUiarleer-

«Ia

14th

53 ί5 line of Terliindttag with the fs »

in 1200 ropes fass »and 40 ropes Istrtiaabikarboaat at 55 ¹ with« si & ai? Sösimg made of 35 ropes 4

ohlorid Treated in 1OQ ropes of acetone _e S & lang becomes the Mieo & vae

at 40 .- iO ^Q boasted ι ies? pH «» Who $ "wi & $ ssit egoige acid, to 5 g © ° blue dye wi ^ ä aiisgee © lsem _t filtered tttid im. · o Bi ⁹ colors the 0ellnl @@ afaseni in rich blue 9 the height and waseheelrt

Jl

1 fell dee naeli example 10 get®n @ iä £ arb @ toffes becomes la 100 Seilern water dissolved, with the so 'produced solution becomes a

Me to a Sewahesunahmo of 100; ^ - soaked Bae | Tissue is then soaked at 25 ^s with a solution containing tjl rörtriumhydroxiä and 30% llatriumohlorld. containing "up to a Uewifinteaanahme of 10O) S squeezed for 3 minutes with \ Waeserdanpf by" 100 - treated 105 ° »rinsed, 10 .spült minutes gewacohen® in a 0" 2jfigen boiling solution of Triton X-IOO ge "and dried . Eb a rich bluish-red color is obtained »which is extremely washable« and lightfast »

ι 90 98 22/123 2 · _eAD

Z5 ₉ A fell · 5,6-J) la "dno-1" naphthol-5 ~ ettljronic acid <? WftrdSB ale RatriunealB in 200 parts of Waeeer and treated with 20 parts of sodium bicarbonate and a solution of 4- (2 ™ 0hloroethylsuliüoy ■ »ensoylohlorid in 100 parts of acetone DiaioniuaealslOeong coupled, which is obtained from 1? "3 parts of metanilee?"; Eo results in a red dye which is reactive in the old east and has good detergency and effectiveness

1 part de "reaktionefähigen dye it, the men B" iirpi @ l € hergeetellt 1st is pH-tone aufgelttet in 1000 parts Waeeer.mit match 5 at 100 °; a cell tissue weighing 50 fail is immersed in the bath and stirred thoroughly for 15 minutes, 1 part of ferric acid is added, then stirred for 45 minutes at 100 degrees. The tissue is then removed, rinsed and dried. Jansend is colored red - the color has excellent wax resistance and good moisture resistance.

instead of 50 parts of the woolen fabric of the previous example a vylon fabric is used, the hylon becomes similarly filled; the color has similar strength properties.

Example 18

41 parts of the compound with the structural formula

- HH,

909822/1232 ORIGINAL BATHROOM

are filed at 40 ° in 1000 water with a pH of 7.5 dissolved; 20 ropes of Hatrumbl carbonate are added; then a solution of 28 ropes of 3- (2-chloroethylsulfonyl) -bezusoylChlorid » dissolved in 40 ropes acetone »added · A product with the structural formula

\ "x ^ mo _{sc> 2- CH2} _ CH ₂ -Cl

was cancelled. The pH value is lowered to 5 using acetic acid; the blue dye is separated by filtration and dried in the yakuua It dyes wool, hyIon, silk and other polyamide and protein-containing (acidic) fibers in red-blue tones, which are easy to light and washable.

Example 19

1 rope of the dye prepared according to Example 18 is dissolved at 100 ° in 1000 ropes of water with a pH of 6.5; A nylon fabric with 50 ropes is immersed in the solution. This is stirred in the solution at 100 ° for 1 hour, rinsed and dried · It is colored in a navy blue sonron with very good wash and light fastness ·.

Example 20

42 ropes of the bond with the structural formula j

are dissolved at 25 ° in 600 ropes of water (neutral) and an-80hlieeeend under good control with 40 ropes of sodium bicarbonate and a solution of 28 ropes of 4- (2-chloroethylsulfonyl) -> bensoylchlorids treated in 150 ropes of acetone · Naoh some Minutes there are no free amino groups. Then one will

909822/1232 ^y

BATH

,. ₂₁ . HU611

Solution of 41 parts of the connection with the structural mold

CXX)

0 HI - /

Waiser with a pH value of 7.0 added on 600 ropes; the The resulting solution is heated to 100 ° and kept at this temperature for 4 hours. "A solution of 25 lines of copper" sulfate pentahydrate in 100 parts of water is carefully added, and the resulting slurry is heated for an additional hour. The resulting green dye is filtered and dried · Sr dyes natural and synthetic polyamide fibers in rich, green ionon and forms the copper complex of the paraffin with the structural forum

909822/1232

BATH ORIGINAL

Claims (12)

Claims 1·. Use of meta and para substituted compounds old the structural formula: MR γ- ^s ° ² - rr In the ft the Badikal is -H or a lower alkyl radical, as activating or articulating reagent preventative for textiles. 2. Use according to claim 1, characterized in that the compound 3- (2-chloroethyleulphonyl) benzoylochloride is used let 3. Use according to claim 1, characterized., aeichnet that the compound 4- (2-chloroethylsulfonyl) benzoylochloride is. 4 · Use of a derivative 4- (2 * haloethylsulfonyl) benzoyl halide with the ladikali as activating or limb-forming Beagenss, preferably for Textiles. 5 · Use of a derivative of a 3- (2-haloethylaulfonyl) -evenyl halide with the radical as an activating or limb-forming reagent, preventive for Textiles. 909822/1232 BATH 6. Use a connection bit of structural formula j E R I I HSO ₂ -O-CMJl C * »0 RR
A. in the & the radical -H or a lower alkyl radical and A let a Textilsueataetoff, which has a functional group is attached, where a hydrogen atom is displaced ”and in which the ring substituents are meta or para to one another as an activating or link-forming reagent for textiles. 7 · Use of a connection with the structural formula » AC- (3 HSO ₂ -OH ₂ -OH ₂ -Cl in which A is a fill additive that has a functional Group is attached from which a hydrogen atom is displaced irt, as an activating or link-forming reagent for textiles 8 Application according to claim 7, characterized in that the textile additive is a dye 9 · Use of a connection with the structural formula: ^ -8O ₂ -CH ₂ -CH ₂ -Cl in which A is the radical of a textile additive, the over a functional · group is attached «from which a hydrogen atom displaced 1st, as an activating or limb-forming reagent for textiles. 909822/1232 ORIGlNAL BATHROOM UU611 10 «Use according to claim 9, characterized in that ~ i without t that the sextile additive is a dye. 11. Use of a meta or para substituted compound with the structural formula 'a ι \ -so ^ -co-ci SR in which E is the radical -E or a lower J scyl radical and Z is the substituent *. -C-A or -C group, and _s is where A is a Sextilssusatzstoff, which is attached through a functional group from which a hydrogen atom has been displaced, · and B is a bed, the iet formed by a textile auxiliary material of at condensation with a carbonyl a fceterosyklisehes System , as an activating or link-forming reagent for textiles. 12. Use of a meta or para substituted compound with the structural formula: R R in which £ the radical -H or a lower alkyl radical _t A is a textile additive which is attached via a functional "group from which a hydrogen atom" is displaced "and X is the radical of a material" which is attached via a functional group from outside a Y / asseratoffatoffi is displaced as an activating or limb-forming reagent for sextiles. 15 «Use according to claim 12, characterized in that that the xextile additive is a dye. 909 8 2 2/1232 14 · Use according to claim 12, characterized «• is worth the fact that T means a cellulose fiber · 15.Using a compound with the structural formula: in which A is a textile additive »the one above a functional one Group is attached »from which a hydrogen atom is displaced, as an active or limb-forming reagent for textiles, 16 Using a compound with the structural formula: in which A is the radical of a textile additive a functional group is attached, as an activating or member-forming reagent for textiles 17. Using a compound with the structural formula: in which A * is a dye attached via a functional group λ from which a hydrogen atom is displaced, as an activating or member-forming reagent for textiles. 18 · Use of a connection with the structural form A'-C-Λγ SO ₂ -OH ₂ -OH ^ -Cmiellulose in which A * is a dye which has a functional group attached 1st, from which a hydrogen atom is displaced, as an activating or link-forming reagent for textiles « 909822/1232 "UU611 19 ·) Process for the production of textile additives that govern fabric, characterized in that, under approximately neutral conditions, a lextilzusatzsteff with a functional group, from which the chlorine of a Carbonylohlorida can be replaced, and a meta- or parasubstituted compound with the structure »fonael _RR l I
O Oil
-SO ₉ -OC-Cl
² II be reacted in which R is the radical -H or a lower alkyl radical 20. The method according to claim 19 »characterized in that that the textile additive contains a dye an amino group is '' 21. A method for attaching a textile additive, the one 'Has functional group of which the: chlorine of a carbonyl chloride is replaceable on textile fibers, which is a functional one Have group reactive with a chloroalkylsulfonyl group is characterized in that under approximately neutral conditions of the textile additive with a meta- or para-substituted compound with the structural formula for Eeaktiott is brought:. in which R is the radical -Q or a lower alkyl radical, so that a derivative arises with the structural formula: HR ₂
ό «ο ^HR A 90.9822 / 1232 H44611 • 27 - in which A is the xueate substance which has a functional group attached let »from which a hydrogen atom is displaced, that the derivative is applied to the textile fiber and that the Derivative and the textile fiber react «so that a connection from which Jormel arises! O- In the f represents a sex fiber, the over a fractional Group attached 1st, from which a hydrogen atom is displaced. 22. Terfahren naoh claim 21, characterized thereby, that the functional group of the additive ea is an amine 23 · Method according to claim 21, characterized in that that the textile fiber is oelluloseartis and that the reaction of the dorivate hastened the fiber in the presence of one Acid blinding takes place. 24 Terfahren according to claim 23, characterized in that that the derivative is water-soluble, and that the reaction takes place between the derivative and the textile fabric in the presence an acid binder and a change inhibitor takes place 25 · Terfahren naoh Claim 21, daduroh know rewarded, that the textile fiber contains functional amino groups. 26 · Use of a compound with the structural formula in which A ", and A" represent different dyes, each There are no functional groups attached * from the '..' ae ο first off atom displaces i3t, as activating or articulating «Ir textiles. UU611 27 Applying a compound with the structural formula IV
ο in which A 'and A ¹³ mean different dyes which are each attached via a functional group from which a W'aB a er at off atom is displaced. 28 «Use according to claim 12, characterized in that · without the fact that T is a fiber that is a functional one Contains amino group * Hel / fü / sol
July 12, 1963 909822/1232