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The action of chlorine upon di-and tri-oxybenzenes has been carefully investigated by Th. Zincke; and his researches have led to the discovery of many chlorinated oxidation products which admit of decomposition into cyclic compounds containing fewer carbon atoms than characterize the benzene ring, and in turn yielding open-chain or aliphatic compounds. In general, the rupture occurs between a-keto group (CO) and a keto-chloride group (CCl2), into which two adjacent carbon atoms of the ring are converted by the oxidizing and substituting action of chlorine. Decompositions of this nature were first discovered in the naphthalene series, where it was found that derivatives of indene (and of hydrindene and indone) and also of benzene resulted; Zincke then extended his methods to the disintegration of the oxybenzenes and obtained analogous results, R-pentene and aliphatic derivatives being formed (R- symbolizing a ringed nucleus).

When treated with chlorine, pyrocatechol (1.2 or ortho-dioxybenzene) (1) yields a tetrachlor ortho-quinone, which suffers further chlorination to hexachlor-o-diketo-R-hexene (2). This substance is transformed into hexachlor-R-pentene oxycarboxylic acid (3) when digested with water; and chromic acid oxidizes this substance to hexachlor-R-pentene (4). The ring of this compound is ruptured by caustic soda with the formation of perchlorvinyl acrylic acid (5), which gives on reduction ethidine propionic acid (6), a compound containing five of the carbon atoms originally in the benzene ring (see Zincke, Ber., 1894, 27, p. 3364) (the carbon atoms are omitted in some of the formulae).

EB1911 Chemistry - ethidine propionic acid.jpg

Resorcin (1.3 or meta dioxybenzene) (1) is decomposed in a somewhat similar manner. Chlorination in glacial acetic acid solution yields pentachlor-m-diketo-R-hexene (2) and, at a later stage, heptachlor-m-diketo-R-hexene (3). These compounds are both decomposed by water, the former giving dichloraceto-trichlor-crotonic acid (4), which on boiling with water gives dichlormethyl-vinyl-a-diketone (5). The heptachlor compound when treated with chlorine water gives trichloraceto-pentachlorbutyric acid (6), which is hydrolysed by alkalis to chloroform and pentachlorglutaric acid (7), and is converted by boiling water into tetrachlor-diketo-R-pentene (8). This latter compound may be chlorinated to perchloracetoacrylic chloride (9), from which the corresponding acid (10) is obtained by treatment with water; alkalis hydrolyse the acid to chloroform and dichlormaleic acid (11).

EB1911 Chemistry - dichlormaleic acid.jpg

Hydroquinone (1.4 or para-dioxybenzene) (1) gives with chlorine, first, a tetrachlorquinone (2), and then hexachlor-p-diketo-R-hexene (3), which alcoholic potash converts into perchloracroylacrylic acid (4). This substance, and also the preceding compound, is converted by aqueous caustic soda into dichlormaleic acid, trichlorethylene, and hydrochloric acid (5) (Th. Zincke and O. Fuchs, Ann., 1892, 267, p. 1).

EB1911 Chemistry - dichlormaleic acid, trichlorethylene, and hydrochloric acid (5).jpg

Phloroglucin (1.3.5-trioxybenzene) (1) behaves similarly to resorcin, hexachlor [1.3.5] triketo-R-hexylene (2) being first formed. This compound is converted by chlorine water into octachloracetylacetone (3); by methyl alcohol into the ester of dichlormalonic acid and tetrachloracetone (4); whilst ammonia gives dichloracetamide (5) (Th. Zincke and O. Kegel, Ber., 1890, 23, p. 1706).

EB1911 Chemistry - Phloroglucin (1.3.5-trioxybenzene) (1).jpg

When phenol is oxidized in acid solution by chlorine, tetrachlorquinone is obtained, a compound also obtainable from hydroquinone. By conducting the chlorination in alkaline solution, Reduction in alkaline solution. A. Hantzsch (Ber., 1889, 22, p. 1238) succeeded in obtaining derivatives of o-diketo-R-hexene, which yield R-pentene and aliphatic compounds on decomposition. When thus chlorinated phenol (1) yields trichlor-o-diketo-R-hexene (2), which may be hydrolysed to an acid (3), which, in turn, suffers rearrangement to trichlor-R-pentene-oxycarboxylic acid (4). Bromine water oxidizes this substance to oxalic acid and tetrabrom-dichloracetone (5).

EB1911 Chemistry - oxalic acid and tetrabrom-dichloracetone (5).jpg

The reduction of o-oxybenzoic acids by sodium in amyl alcohol solution has been studied by A. Einhorn and J. S. Lumsden (Ann., 1895, 286, p. 257). It is probable that tetrahydro acids are first formed, which suffer rearrangement to orthoketone carboxylic acids. These substances absorb water and become pimelic acids. Thus salicylic acid yields n-pimelic acid, HOOC·(CH2)5·COOH, while o-, m-, and p-cresotinic acids, C6H3(CH3)(OH)(COOH), yield isomeric methylpimelic acids.

Resorcin on reduction gives dihydroresorcin, which G. Merling (Ann., 1894, 278, p. 20) showed to be converted into n-glutaric acid, HOOC·(CH2)3·COOH, when oxidized with potassium permanganate; according to D. Vörlander (Ber., 1895, 28, p. 2348) it is converted into γ-acetobutyric acid, CH3CO·(CH2)3·COOH, when heated with baryta to 150-160°.

Configuration of the Benzene Complex.—The development of the “structure theory” in about 1860 brought in its train an appreciation of the chemical structure of the derivatives of benzene. The pioneer in this field was August Kekulé, who, in 1865 (Ann., 137, p. 129; see also his Lehrbuch der organischen Chemie), submitted his well-known formula for benzene, so founding the “benzene theory” and opening up a problem which, notwithstanding the immense amount of labour since bestowed upon it, still remains imperfectly solved. Arguing from the existence of only one mono-substitution derivative, and of three di-derivatives (statements of which the rigorous proof was then wanting), he was led to arrange the six carbon atoms in a ring, attaching a hydrogen atom to each carbon atom; being left with the fourth carbon valencies, he mutually saturated these in pairs, thus obtaining the symbol I (see below). The value of this ringed structure was readily perceived, but objections were raised with respect to Kekulé’s disposal of the fourth valencies. In 1866 Sir James Dewar proposed an unsymmetrical form (II); while in 1867, A. Claus (Theoretische Betrachtungen und deren Anwendung zur Systematik der organischen Chemie) proposed his diagonal formula (III), and two years later, A. Ladenburg (Ber., 2, p. 140) devised his prism formula (IV), the six carbon atoms being placed at the six corners of a right equilateral triangular prism, with its plane projections (V, VI).

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One of the earliest and strongest objections urged against Kekulé’s formula was that it demanded two isomeric ortho-di-substitution derivatives; for if we number the carbon atoms in cyclical order from 1 to 6, then the derivativesObjections to Kekulé’s formula. 1·2 and 1·6 should be different.[1] Ladenburg submitted that if the 1·2 and 1·6 compounds were identical, then we should expect the two well-known crotonic acids, CH3·CH:CH·COOH and CH2:CH·CH2·COOH, to be identical. This view was opposed by Victor Meyer and Kekulé. The former pointed out that the supposed isomerism was not due to an arrangement of atoms, but to the disposition of a valency, and therefore it was doubtful whether such a subtle condition could exert any influence on the properties of the substance. Kekulé answered Ladenburg by formulating a dynamic interpretation of valency. He assumed that if we have one atom

  1. It is now established that ortho compounds do exist in isomeric forms, instances being provided by chlor-, brom-, and amino-toluene, chlorphenol, and chloraniline; but arguments, e.g. E. Knoevenagel’s theory of “motoisomerism,” have been brought forward to cause these facts to support Kekulé.