Synthesis of Reactive Dyes

Virtually every conceivable chromophore has been used in the synthesis of reactive dyes, including monoazo and disazo species, metal complexes of azo dyes, formazan dyes, anthraquinones, triphenodioxazines, and phthalocyanines. The product lines offered by the major dye producers in most cases feature comparable chromophores, differing primarily in the nature of the reactive systems and the particular substitution patterns adopted. 

The chlorosulfonation of the CuPc system opens the door to the synthesis of reactive dyes, as shown in Fig. 13.137. In this case, aminochlorotriazine 56 reacts with a CuPc-S02Cl intermediate to give a mono-chlorotriazine reactive dye (57), which in turn can be used to make the cationic reactive dye 58. 

Shen X M, FT-IR andNIR FT-Raman On-line Measurement of the Synthesis of Reactive Dyes, PhD Thesis, University of Leeds, 1998. 

The synthesis of vinylsulfonyl dyes is a good example for a method to obtain pH indicator layers with operational stability of weeks and shelf life of years. Commercial transparencies with a cellulose coating are used as the polymer matrix and the reactive vinylsulfonyl dye is bound to the cellulose... 

Azo dyes are by far the largest family of organic dyes. They play a prominent role in acid, direct, reactive, azoic, and disperse dye structures, as shown previously, and include structures that cover the full color spectrum. Generally, the synthesis of azo dyes involves a process known as diazo coupling. In this... 

The side-chain reactivity of the pyrylium ion facilitates a targeted synthesis of cyanine dyes with pyrylium or 4//-pyran systems as terminal groups (see p 323). In this way, the dye 60 is produced by ViLSMElER formylation of the 4-methylpyrylium ion 58 to give the formylmethylene-4//-pyran 59 followed by aldol condensation with a second molecule of 58 [10] ... 

Monoazathiazolocyanines (Tables 2171A.B). The same reactive intermediates and the same conditions as in the case of thiazolomethine dyes are used in the synthesis of this class of dyes, except that the CH group is replaced by a -NH group (Schemes 46 and 47). No j3-azatrimethine thiazolocyamne has been described, in spite of an access method applied with success to other rings (65). 

Fluorination and iodination reactions are used relatively littie in dye synthesis. Fluorinated species include the trifluoromethyl group, which can be obtained from the trichi oromethyl group by the action of hydrogen fluoride or antimony pentafluoride, and various fluorotria2iQyl and pyrimidyl reactive systems for reactive dyes, eg, Cibacron F dyes. 

Phenazine leucos until now are usually substituted at their 3 and 6 positions by amino groups due to the normal method of synthesis of the parent phenazine dyes. These types of leuco dyes are reactive. An alternative method of dye synthesis allows access to phenazine dyes with just one substituent at the 3-position.20 The resulting leuco dyes are called half diazine leucos. The loss of one exocyclic amino group leads to higher redox potential and results in less reactive leuco dyes, more useful in applications such as thermographic and photothermographic imaging, particularly Color Dry Silver. 

In Chapters 3-6, the commercially important chemical classes of dyes and pigments are discussed in terms of their essential structural features and the principles of their synthesis. The reader will encounter further examples of these individual chemical classes of colorants throughout Chapters 7 10 which, as a complement to the content of the earlier chapters, deal with the chemistry of their application. Chapters 7, 8 and 10 are concerned essentially with the application of dyes, whereas Chapter 9 is devoted to pigments. The distinction between these two types of colorants has been made previously in Chapter 2. Dyes are used in the coloration of a wide range of substrates, including paper, leather and plastics, but by far their most important outlet is on textiles. Textile materials are used in a wide variety of products, including clothing of all types, curtains, upholstery and carpets. This chapter deals with the chemical principles of the main application classes of dyes that may be applied to textile fibres, except for reactive dyes, which are dealt with exclusively in Chapter 8. 

The most commonly employed routes for the preparation of the / -sulfatoethylsulfone group, which is the essential structural feature of vinylsulfone reactive dyes, are illustrated in Scheme 8.5. One method of synthesis involves, initially, the reduction of an aromatic sulfonyl chloride, for example with sodium sulfite, to the corresponding sulfinic acid. Subsequent condensation with either 2-chloroethanol or ethylene oxide gives the / -hydroxyethylsulfone, which is converted into its sulfate ester by treatment with concentrated sulfuric acid at 20 30 °C. An alternative route involves treatment of an aromatic thiol with 2-chloroethanol or ethylene oxide to give the /Miydroxyethylsulfonyl compound which may then be converted by oxidation into the /Miydroxyethylsulfone. 

Oswald B, Patsenker L, Duschl J, Szmacinski H, Wolfbeis OS, Terpetschnig E (1999) Synthesis, spectral properties, and detection limits of reactive squaraine dyes, a new class of diode laser compatible fluorescent protein labels. Bioconjugate Chem 10 925-931... 

Fluorophores are relative small molecules that, with some exceptions, are not naturally occurring and have to be synthesized chemically. There has been a large development in the synthesis of fluorescent molecules and nowadays there is a vast range of alternatives including dyes with improved photochemical properties, solubility or modified reactivity that allow for conjugation to other molecules of interest and the synthesis and application of fluorescent sensors [10, 13], Although a lot is known about the physics of fluorescence and a lot of information is available about the properties of dyes, their prediction from the chemical structures cannot be accurately done. For this reason, there has been a... 

Makedonski P., Brandesa M., Grahnb W., Kowalsky W., Wichem J., Wiese S., Johannes H., Synthesis of new kinds of reactive azo dyes and their application for fibre-optical pH-measurements, Dyes and Pigments 2004 61 109-119. 

Heavy metals are widely used as catalysts in the manufacture of anthraquinonoid dyes. Mercury is used when sulphonating anthraquinones and copper when reacting arylamines with bromoanthraquinones. Much effort has been devoted to minimising the trace metal content of such colorants and in effluents from dyemaking plants. Metal salts are used as reactants in dye synthesis, particularly in the ranges of premetallised acid, direct or reactive dyes, which usually contain copper, chromium, nickel or cobalt. These structures are described in detail in Chapter 5, where the implications in terms of environmental problems are also discussed. Certain basic dyes and stabilised azoic diazo components (Fast Salts) are marketed in the form of tetrachlorozincate complex salts. The environmental impact of the heavy metal salts used in dye application processes is dealt with in Volume 2. 

In the outstandingly successful Cl Reactive Black 5, two such precursor-bearing units are used in the synthesis of this near-symmetrical bifunctional structure (7.36). Following this precedent, competing bifunctional dyes of analogous structure were designed with two phenylene-l,3-diamine-4-sulphonate groupings to accommodate the reactive systems... 

Because of the relatively low sensitivity of TLC methods they have not been frequently applied for the analysis of samples containing trace amounts of synthetic dyes. However, TLC techniques have been proven to be a rapid, reliable and valuable tool for the easy following of synthetic procedures for the preparation of new dyes. Thus, the synthesis of some bifunctional reactive triazine dyes has been monitored by TLC. The synthetic pathways a and b are shown in Fig. 3.12. The purity of intermediates was controlled by TLC using a silica stationary phase (Rp value of 2-allylamino-4,6-chloro-l,3,5-triazine = 0.48... 

Normal-phase TLC has been employed for the control of the synthesis of some new reactive azo dyes containing the tetramethylpiperidine fragment. The chemical structure of the basic molecule and the substituents of the new derivatives are shown in Fig. 3.16. The new derivatives were characterized by their RF values determined in different mobile phases. Compositions of mobile phases were n-propanol-ammonia (1 1, v/v) for dye 1.2 (Rp = 0.84) n-propanol-ammonia (2 1, v/v) for dyes 1.3 (RF = 0.50) and 1.4 (RF = 0.80) and n-heptane-diethyl ether (1 1, v/v) for dyes 1.5 (RF = 0.80) and 1.6 (RF = 0.76). The results indicated that together with other physicochemical methods such as IR and H NMR, normal-phase TLC is a valuable tool for the purity control and identification of new synthetic dyes [96],... 

T. Konstantinova and P. Petrova, On the synthesis of some bifunctional reactive triazine dyes. Dyes Pigm. 52 (2002) 115-120. 

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