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This article is cited by 2 publications. Kenneth M. Harmon, Thomas T. Coburn. Carbonium ion salts. XII. Thermodynamic and infrared spectral studies on.
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Ordinarily, from its solutions in alkalies, aurin is precipitated as the fuchsone, whether the alkali be dilute or concentrated, cold or hot, whether the precipitation be accomplished by just neutralizing with acetic acid, or adding an excess of the latter, or whether the dye be precipitated by passing carbon dioxide into the solution. When hydrochloric acid is used, then if the amount of acid added is just enough to neutralize the al- kali, fuchsone is the result; when a considerable excess of acid is added, the fuchsone is contaminated with some fuchsone hydrochloride.

The Condensation of Carbon Tetrachloride and Phenol : Aurin (Classic Reprint)

We have finally succeeded in getting the desired hydrated carbinol by observ- ing the following conditions. Aurin is dissolved in sodium hydroxide and to the warm solution 60 to 70 is slowly added dilute hydro- chloric acid, while the solution is well stirred. At the neutral point, the 12 precipitate consists of light red fuchsone, but when a slight excess of acid is added and the stirring of the warm solution is continued for 15 minutes, the red fuchsone soon turns to fine purple threads consisting almost entirely of hydrated aurin. A sample of such a product was dried on a porous plate for 24 hours, powdered and air-dried for several hours longer.

A weighed amount of the substance was then dehydrated by pass- ing over the sample in a porcelain boat dry air at room temperature and finally heating to A gradual loss of water occurred 1 mol.

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The slight excess of hydrochloric acid over that necessary for the neu- tralization of the alkali in the preparation of aurin hydrate probably forms a correspondingly small amount of aurin hydrochloride. This gradually becomes hydrolyzed to aurin hydroxide and the liberated acid continues to act in the same manner as before until all of the aurin is changed to the carbinol.

On prolonged standing, espe- cially at low temperature, fuchsone is the product. Ten g. The yield of the crude product was 14 g.

References

One recrystallization from alcohol gave 13 g. The pure compound melts at His results could not be verified; a single product with a definite melt- ing point of was obtained by us. To a solution of 15 g. The solution soon turns pink and on longer standing the chloride separates in well-formed, slightly colored crystals which carry benzene of crystallization in the ratio of one molecule of benzene to one molecule of the chloride.

When the compound is digested with absolute ether, it still retains most of the benzene. The chloride can, however, be obtained free from solvent when the fine crystalline prod- uct is heated at 78, under reduced pressure, in a stream of air dried over phosphorus pentoxide. The compound turns yellow when heated, begins to soften at and melts at to a red liquid with the evolution of acetyl chloride.

Found: 7. The chloride begins to give off acetyl chloride at , more rapidly at , until one molecule of acetyl chloride has been lost. By the action of molecular silver upon the 9 a Graebe and Caro, Ber. This free radical is very unstable and was not isolated. The fact of its transitory existence was established by the isola- tion of the corresponding peroxide. Quantitative determinations of the amount of oxygen that is absorbed by the free radical were made by sealing the chloride and silver with a solvent, in a test-tube, shaking at room temperature for a definite time, and then measuring the amount of oxygen that the solution absorbs.

The peroxide was recrystallized from methylethyl ketone. It melts at to a red liquid. To 10 g. The resulting mixture was washed first with dil. The yield after one recrystallization of the crude material from benzene was 13 g. The compound melts at This substance surpasses even aurin itself in the singular property of combining generally with solvents from which it is crystallized. It is difficult to find an explanation why this carbinol, structurally saturated, should possess even more residual affinity than aurin, which is structurally unsaturated.

The following combinations have been obtained. To a solution of 10 g. After several hours the mixture was warmed gently in order to bring into solu- tion the carbinol chloride which had precipitated, and the calcium chloride was filtered off. The solution was concentrated and absolute ether added.


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The chloride precipi- tated in white crystals carrying benzene of crystallization, 1 molecule of the solvent to 1 of the chloride. It loses the solvent of crystallization when heated to temperatures slightly above the boiling point of benzene and melts at to a red liquid. Found: 5. OCCeHsV As in the case of the acetyl compound, it is necessary to prepare this peroxide by the simultaneous action of silver and oxygen upon the chloride in solution; otherwise, the radical decomposes to a large extent prior to the oxidation process. When crystal- lized from chloroform it carries solvent of crystallization which it retains very firmly.

After drying at the compound when further heated melts at to a red liquid. Decomposition of Aurin by Air and Alkali. Aurin can be oxidized by atmospheric oxygen in the presence of alkalies with much greater ease than has been usually assumed. Fusion is not necessary. The filtered solution gave, on the addition of acetic acid, 5. Isolation of Leuco-aurin from the Condensation Product. The origin of this prod- uct in the reaction mixture has been explained on p.

It is to be found in the ether extract of that fraction of the mixture which is insoluble in dil. The moist ether extract is saturated with hydrogen chloride, decanted from the resulting precipitate and evaporated to dryness. The residue ob- tained on the evaporation of ether consists of leuco-aurin mixed with a small amount of substance Z which still remains unidentified. The leuco compound is purified by recrystallization from chloroform and benzene, in which mixture the product Z is more soluble than the former.

The leuco compound was identified by analysis and by a comparison of it with leuco-aurin which was prepared directly from pure aurin by reduction with zinc dust and acetic acid. Furthermore, each of the two samples was acetylated, and they gave the identical triacetyl-leuco- aurin; 13 m. As mentioned in the preceding para- graph, this compound is to be found together with leuco-aurin.

When the ether extract that contains these two substances is saturated with hydrogen chloride, the o, p', p"- trihydroxy carbinol forms an insoluble carbinol-chloride, which on treatment with alkali gives the carbinol, or its anhydride the fuchsone. This, however, contains some im- purity which is not easily separated. Freshly precipitated, the almost colorless carbinol changes rapidly to a red powder which is soluble in ether; when the product is dried, it is rendered insoluble in ether. We have failed to obtain the carbinol in crystalline form to be identified directly as such.

Methylation, benzoylation and acetylation also failed to give rise to products that could be crystallized. We then reduced our crude carbinol with zinc and acetic acid to the corresponding leuco base, and after preliminary purification of it from benzene and petroleum ether, we methylated it by means of di- methyl sulfate. The resulting substance, m. The Grignard reagent was prepared from o-iodo-anisole in ether. The insoluble mag- nesium compound of the earbinol was filtered off, washed with benzene, and decomposed 11 a Caro and Graebe, Ber.

The carbinol, recrystallized from benzene and petroleum ether, melted at This was prepared from the carbinol described by reduction with zinc dust at The product was recrystallized from petroleum ether.

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It melted, like the methane from the carbinol in the condensation mixture, at A mixture of the two methane samples, which came from the two different sources, also melted at The separation of the two is therefore readily accomplished. The xanthane was recrys- tallized from ether and petroleum ether and melted at to with decomposition. For further identification our hydroxy-xanthane was methylated by means of dimethyl sulfate and the methoxy derivative compared with -methoxyphenyl-xanthane obtained directly from the corresponding xanthenol 14 by reduction with zinc dust.

The two proved identical, each sample of the xanthane melting at Unlike the latter, it is not soluble in dil. It is separated from other products as indicated on p. After this treatment the product is a light orange powder and is quite pure. It gives with alkali a red color bordering on orange, while aurin gives a pure red solution. The fluorone is insoluble in the usual organic solvents except acetic acid, from which it crystallizes in orange-red crystals.

It melts at with the evolution of phenol. C6H 4 O. COCH, To 5 g. After two days, the mixture was poured into water and the precipitated mass was washed with alkali and water. The 14 Gomberg and West, J.


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The mono-acetyl compound was obtained crystalline and pure from its concentrated solution in benzene by adding a large volume of ether. It melts at The diacetyl compound was obtained also in white crystals by adding to its solution in benzene a large volume of carbon disulfide; m. Mono-acetyl compound. Diacetyl compound. The monomethoxy derivative was crystallized from benzene and from acetone and the orange-colored crystals melted at The compound described proved to be identical in every way with the p-methoxy- phenyl-fluorone prepared by Grignard's reaction from 3-hydroxyxanthone 15 and p- anisylmagnesium iodide.

The dimethoxy derivative, recrystallized from alcohol and then from benzene, melted at This, like our product from the condensation reaction, melted at The two on treatment with acetyl chloride gave identical, colored carbinolchloride-hydrochlorides melting at The -methoxyphenyl-fluorone, pre- pared by Grignard's reaction as described above, was demethylated by aluminum chlor- ide in antimony trichloride as the solvent. After purification, the product proved to be identical in every respect with the compound obtained in the condensation reaction.

It melted at with the evolution of phenol. Oxidation by Air and Alkali. A solution of 10 g. Direct introduction of an aldehyde group is Lit o an aromatic nucleus is limited to the Gattermann , Gattermann-Koch 40 , Vilsmeier 51 Duff 49, 75 , and Reimer-Tiemann reactions.

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All but the ReimerTiemann reaction are conducted under acidic and anhydrous conditions. Only the Gattermann and Duff reactions are applicable to phenols. Since in the Gattermann reaction the entering aldehyde group usually occupies a position para to the hydroxyl group, while the Duff reaction fails with polyhydric phenols and phenols carrying negative substituents, the ReimerTiemann reaction is occasionally the only method for the direct ortho formylation of phenols.

Thus 2-nitrophenol , pyrrole, and indole, which do not furnish aldehydes in a Gattermann reaction , are formylated successfully under Reimer-Tiema:ln reaction conditions. The sodium salt of the hydroxyaldehyde frequently separates from the concentrated solution as the reaction proceeds.