Phthaleins

The phthaleins are derivatives of triphenylmethane, and form a group of dyestuffs which are sharply defined from the rosaniline and rosolic acid derivatives already described. In the latter the chromophorous groups are in para positions, while in the former two adjacent positions are taken up. 

With respect to the colour-giving group, there is a certain analogy between these dyestuffs and those of the Indigo series, these latter being characterised by the lactam or lactim ring — 

The phthaleins are all derivatives of phthalophenone, the inner anhydride of triphenylcarbinolcarbonic acid  

This acid is not capable of existing in a free state, but may be obtained in form of its salts. The relationship between phthalophenone and triphenylmethane is easily determined. By treatment with alkalies it yields triphenylcarbinolcarbonic acid, and this may be converted to triphenylmethanecarbonic acid by reduction with zinc powder. On heating this latter compound, carbon dioxide splits off, forming triphenylmethane. 

Phthalophenone is not a dyestuff, the tinctorial character only becoming apparent on introduction of hydroxyl groups into both phenyl groups. 

---

It condenses with resorcinol and amino-phenols to give phthalein and rhodamine dyestuffs respectively. Esters are used in the formation of polyimides. ... 

NOTE. It is not expected that a student xvill attempt to memorise all the colour tests given in Part III. He might for example be expected to know the Phthalein Reaction for phenol itself (p. 339). Details of the divergence from the standard result are recorded primarily for reference, so that a student will not be diverted from his line of investigation if he observes that a suspected phenol does not respond exactly to the standard colour changes. 

Phthalein reaction. Place in a dry test-tube about 0 2 g. of the phenol and an equal quantity of phthalic anhydride (or acid), moisten with 2 drops (not more) of cone. H2SO4 and gently fuse together for about 1 minute. Allow to cool somewhat, and then add 10% NaOH solution in excess. 

Does not form a phthalein or fluorescein (distinction from phthalic acid). 

Phthalein formation Fuse together carefully in a dry test-tube a few crystals of salicylic acid or of a salicylate with an equal quantity of phthalic anhydride rnoistened with 2 drops of cone. HjSO. Cool, dissolve in water and... 

C) Phenacyl and p-Bromophenacyl esters. Ammonium salts in aqueous-ethanolic solution do not however usually condense satisfactorily with phenacyl and />-bromophenacyl bromide. The aqueous solution of the ammonium salt should therefore be boiled with a slight excess of sodium hydroxide to remove ammonia, and the solution then cooled, treated with hydrochloric acid until just alkaline to phenol-phthalein, and then evaporated to dryness. The sodium salt is then treated as described (p. 349) to give the ester. Filter the ester, and wash with water to remove senium halide before recrystallisation. 

The fluorescein test for succinic acid (p. 349) and the phthalein and fluorescein tests for phthalic acid (p. 351) are obviously given also by succinic anhydride and phthalic anhydride, as these tests depend upon the initial formation of the anhy dride in each case. 

Benzylthiouronium salts. Add 0 5 g. of sulphanilic acid to 10 ml. of water and 5 ml. of 10% NaOH solution, zndgently warm the shaken mixture until a clear solution is obtained. Cool, add 1 drop of phenol-phthalein solution, and then add dilute HCl dropwise with shaking until the pink colour is just discharged. Now add very dilute NaOH solution until the pink colour yt/rZ returns. Cool and add with shaking a solution of 0-5 g. of benzylthiouronium chloride in 5 ml. of water. The thiouronium salt rapidly separates filter at the pump, wash with water, drain and recrystallise from ethanol. Colourless crystals, m.p. 185°. (M.ps., p. 548.)... 

Phthaleins (Phthalic anhydride TH SO.) red green fluorescence usually blue purple red blue- purple — green faint green fluorescence... 

Special reactions — — — Fluores- cein Iodoform (KI + NaClO) FeSO, + H.O, + NaOH violet — — — (a) Fluores- cein W Phthalein —... 

The method is based on the conversion of urea to amnionium carbonate and the estimation of the latter by titration with standard acid. For this purpose, two equal quantities of urea (or urine) are measured out into two flasks A and B. A is treated with 10 ml. of a strong urease preparation and some phenol-phthalein, warm water is added and the mixture is adjusted by the addition of V/io HCl from a burette A until the red colour is just discharged. This brings the mixture to about pH 8 (the optimum for urease) and also prevents loss of ammonia. 

The above simple experiments illustrate the more important properties of aliphatic acid chlorides. For characterisation, the general procedure is to hydrolyse the acid chloride by warming with dilute alkali solution, neutralise the resulting solution with dilute hydrochloric acid (phenol-phthalein), and evaporate to dryness on a water bath. The mixture of the sodium salt of the acid and sodium chloride thus obtained may be employed for the preparation of solid esters as detailed under Aliphatic Acids, Section 111,85. The anilide or p-toluidide may be prepared directly from the acid chloride (see (iii) above and Section III,85,i). 

Similarly o-sulphobeiizoic anhydride and o-cresol yields o-cresolsulphone-phthalein (o-cresol red) dibromination of the last-named gives dibromo-o-sulphonephthaleln (bromocresol purple) ... 

Ethyl bis-(2,4-dinitrophenyl) acetate (indicator) the stock solution is prepared by saturating a solution containing equal volumes of alcohol and acetone with the indicator pH range colorless 7.4-9.1 deep blue. This compound is available commercially. The preparation of this compound is described by Fehnel and Amstutz, Ind. Eng. Chem., Anal. Ed. 16 53 (1944), and by von Richter, Ber. 21 2470 (1888), who recommended it for the titration of orange- and red-colored solutions or dark oils in which the endpoint of phenol-phthalein is not easily visible. The indicator is an orange solid which after crystallization from benzene gives pale yellow crystals melting at 150-153.5°C, uncorrected. 

For uniformity with the stmctures given in the Colourindex the ammonium radical (9) is used for the amino-substituted xanthenes and the keto form for the hydroxy derivatives. The xanthene dyes may be classified into two main groups diphenylmethane derivatives, called pyronines, and triphenylmethane derivatives (eg, (4)), which are mainly phthaleins made from phthaUc anhydride condensations. A third much smaller group of rosamines (9-phenylxanthenes) is prepared from substituted ben2aldehydes. The phthaleins may be further subdivided into the following fluoresceins (hydroxy-substituted) rhodamines (amino-substituted), eg, (6) and mixed hydroxy/amino-substituted. 

Phthaleins. Dyes of this class are usually considered to be triaryhnethane derivatives. Phenolphthalein [77-09-8] (23, R = CO) and phenol red [143-74-8] (23, R = SO2) are used extensively as indicators in colorimetric and titrimetric determinations (see Hydrogen-ION activity). These compounds are prepared by the condensation of phenol with phthaUc anhydride or i9-sulfoben2oic anhydride, respectively, in the presence of a dehydrating agent. 

Dyes, xanthene used for eosin, fluorescein-type phthaleins, rhodamines, and rose Bengal. 

Remove 10 ml of this solution and add a few (three to five) drops of phenol phthalein and shake. 

To the same solution add a few drops of phenol phthalein, and titrate it against N/10 NaOH until a pink colour appears, which will indicate the total acidity of the bath. This is approximately 35 to 37 for a concentration of 5% for a hot process and 60 to 64 for a concentration of 10% for a cold process. Obtain the standard total acidity of the hot or cold process chemicals from the manufacturer. 

One 1-ml aliquot is added to 1.0 ml of freshly-distilled 1,2-dibromo-ethane (bp 132°C) in an oven-dried flask which contains a static atmosphere of nitrogen or argon. After the resulting solution has been allowed to stand at 25°C for 5 min, it Is diluted with 10 rat of water and titrated for base content (residual base) to a phenolphthalein endpoint with standard 0.100 M hydrochloric acid. The second 1-mL aliquot is added cautiously to 10 ml of water and then titrated for base content (total base) to a phenol phthalein endpoint with standard aqueous 0.100 M hydrochloric acid. The methyllithium concentration is the difference between the total base and residual base concentrations.2 Alternatively, the methynithiura concentration may be determined by titration with a standard solution of sec-butyl alcohol employing 2,2 -bipyridyl as an indicator. 

Purification as for phthalein complexone except that it was synthesised from thymolphthalein instead of cresolphthalein. 

X-Ray diffraction analysis of phthaleine and sulfophthaleine pigments 97YZ764. 

---