Crystal violet synthesis

Michler s ketone (6.155) and related carbonyl compounds can be used to obtain colour salts directly by reaction with a reactive intermediate such as an aromatic amine (the ketone synthesis), as in the case of crystal violet (6.164 Cl Basic Violet 3) shown in Scheme 6.31. 

The product may be obtained from tetraethyldiaminobenzophenone and N-ethylnaphthylamine with phosphorus oxychloride or with phosphorus trichloride, the route parallels the synthesis of Crystal Violet. The resulting colorant is the basic dye for Pigment Blue 1. 

The technical preparation of crystal violet and of its methyl-free parent substance, parafuchsine, almost the oldest of the triphenylmethane dyes, is not so easily explained. As is well known, in this process aniline and p-toluidine are united by oxidation in an acid melt. (In the preparation of fuchsine itself, which contains a methyl group attached to one of the benzene rings, o-toluidine is an additional ingredient.) Although all the phases of this important synthesis have not yet been experimentally established, we may nevertheless explain it on the basis of a dehydrogenation similar to that involved in the formation of malachite green. Moreover, the union of several molecules of base proceeds exactly according to the principle on which indamines are formed (p. 321) (Bucherer). 

While the student is being educated in preparative work it is necessary for him to acquire some knowledge of the incessant progress in the methods of organic chemistry and at the same time to become familiar with the most recent results of research work. For these reasons a series of changes had to be made when this new edition was prepared. In order not to increase the bulk of the book these objects have been attained by sacrificing examples (e.g. lino-lenic acid, crystal violet, Gattermann-Koch aldehyde synthesis) with which, from this point of view, it seemed possible to dispense. 

The poly (ribitol phosphate) synthetase and poly (glycerol phosphate) synthetase are inhibited by vancomycin, novobiocin, and Crystal Violet. Other antibiotic substances which interfere with cell-wall synthesis (such as bacitracin, ristocetin, and streptomycin) are almost without effect on the isolated synthetases, and penicillin is inhibitory at high concentrations only. Moreover, penicillin, vancomycin, and bacitracin do not markedly inhibit synthesis of cell-wall glycosaminopeptide in vitro, although the synthetical activity of extracts of cells which have been pretreated with these antibiotics is lowered.Convincing evidence that the primary site of inhibition by antibiotics is the biosynthesis of cell-wall material has been obtained only for the penicillins and cycloserine, and it appears that the action of even those antibiotics may be more complex than was originally supposed. 

Park and Strominger noticed the accumulation of a C3didine derivative in cultures of Staphylococcus aureus which had been inhibited by chloramphenicol, penicillin, or Crystal Violet. This cytidine derivative has been identified by Baddiley s group as cytidine ribitol pyrophosphate. Since these inhibitors affect the cell-wall synthesis, the data lend support to the belief that the cytidine compound is involved in the biosynthesis of a cell-wall constituent, and a likely candidate would be ribitol teichoic acid. 

Use Organic synthesis, dyestuffs (crystal violet), fumigants, fungicides, insecticides, rat exterminator, tear gas. 

The oxidation of hydroarenes to arenes by quinones such as 2,3-dichloro-5,6-dicyano-l,4-quinone (DDQ) is frequently used for the synthesis of aromatic compounds. Brower et al. have already shown that the dehydrogentaion 1,4-cyclo-hexadiene to benzene [128] or tetraline to naphthalene [129] by thymoquinone is accelerated by pressure giving a negative volume of activation ((AV = —33 (75 °C) and —28 (175 °C) cm mol respectively). A similar effect of pressure has been observed for the oxidation of leuco crystal violet with p-chloranil ((AV = -25 cm mol (21 °C) [130]. The pressure-dependent kinetic isotope effect of this reaction (29 °C kn/ D = H-5 (1 bar) and 8.2 (1.5 kbar)) indicates that hydrogen transfer occurs in the rate-determining step. The large kn/ko value at 1 bar and it pressure dependence was attributed to a quantum mechanical tunneling. 

Zhu, C.F., Wu, A.B., 2005. Studies on the synthesis and thennochromic properties of crystal violet lactone and its reversible thermochromic complexes. Thermochimica Acta 425, 7-12. 

The following example structures help to illustrate the idea of the SPA. Figure 6.25 shows the analysis for crystal violet. The result is a continuous loop of alternating plus-minus connections that is consistent with the synthesis plan for its construction as shown in Figure 6.26. 

In late 1995, a team led by Vollhardt and Youngs reported their work on the strained PAM/PDM hybrid 80 [55]. Whereas the synthesis of 80 was not remarkable [Eq. (2)1, the solid-state behavior of the molecule was. X-ray crystallography revealed that the macrocycle was moderately strained, with the monoynes bent inward toward the center of the macrocycle by 3.9 -11.5° and the diyne unit bent outward by 8.6-11.2°. More importantly, crystal packing revealed that the diyne moieties were aligned in the prerequisite fashion for topochemical diacetylene polymerization to occur. Indeed, irradiation of crystals of 80 produced a violet... 

From about 1930 onwards, developments in the field of naphthoquinone dyes concentrated on the use of naphthazarin and intermediates for the preparation of violet, blue, and green acid and disperse dyes [1]. More recently there has been interest in the synthesis and color and constitution properties of simple colored naphthoquinones, stimulated by the fact that such dyes have similar tinctorial properties to the anthraquinones but a smaller molecular size. The naphthoquinones provide a useful alternative to the anthraquinones for certain specialized applications, e g., as pleochroic dyes with improved solubility for liquid-crystal displays. As a result, research interest in these chromogens remains unabated, even though they have failed to make any major impact as textile dyes [2-8],... 

Monoimine, N-methylated, and semiclathrochelate complexes have been isolated and identified as by-products of sarcophaginate synthesis to gain a deeper insight into the reaction mechanism. The addition of sodium hydroxide to an aqueous solution of [Co(diNOsar)](0104)3 complex leads to a change in the colour of the solution from orange to violet. The violet crystals of the deprotonated [Co(diNOsar-H)] (0104)2 compound were isolated [101]. 

Synthesis and resolution of the [Goa(gly)(tacn)]-type complexes — The terdentate ligand was prepared as its trihydrochloride by the method of Richman and Atkins (29). Equimolar amounts of mer(N)-trans(NH,)-[Co(CO,)(gly)(NH,)2] (30) and tacn-3HC1 were dissolved in water, and the solution was adjusted to pH 2 with HC1C>4 (60%) and then adjusted to pH 9 with aqueous KOH solution, whereupon the color of the solution changed from violet to red, indicating the formation of [Co(gly)(tacn)-(H20)]2+. The purification of the desired complex species was carried out by means of ion-exchange chromatography (SP-Sephadex C-25 in Na+ form and 0.1 M NaClO ). Finally, from an ethanolic solution of the concentrated eluate, red crystals of the aqua complex compound, [Co(gly) (tacn) (H-O) ] (CIO.)-, was obtained. 

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