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73. Determination of Substituent Positions in Hinokitiol

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73. Determination of Substituent Positions in Hinokitiol No. 10.] (10) 25 73. Determination o f Substituent Positions in Hinokitiol Derivatives (I)°. By Tetsuo NozoE, Yoshio KITAHARA,and KOzoDOI. ChemicalInstitute, Facultyof Science,Tohoku University. (Comm. by R. MAJIMA,M.J.A., Dec. 12, 1950.) Hinokitiol, i. e. m-isopropyltropolone,(A: X = H), has a remarkable semiaromatic characteristics and it easily affected by electrophilic reagents. Nozoe and his co-workers' have obtained a large number of derivatives possessingvarious substituents. These compoundsbelong to a series of new types and are difficult to be linked with the known compounds, making it hard to determine the position of their substituents. However, interrelationships between these numerous compounds have begun to become clearer, by the utilization of azo coupling~~and sulfonation,'~ and by the measurement of dipole moments, that substituent positions can now be predicted with a certain amount of accuracy. In substituted hinokitiol derivatives, it is not possible to put too much stress on the results of actual dipole moment measurements since it would be necessary to consider the presence of special stereo- isomers due to the steric position of the isopropyl group and the resonance inhibition. On the other hand, there is a great possi- bility that the substitution reaction is accompanied by the exchange of s ubstituents or an intramolecular rearrangement='>that there is a need for a more reliable confirmation for the structural deter- mination of the products. Of the numerous derivatives of hinokitiol, a large number of nitro compoundshave been isolated and classified. Since the relation- ship between these nitro compounds and other derivatives (amino, halogeno, azo, etc.) are easily established', and because they easily give vitro compounds of m-comic acid, a 6-membered ring compound, by rearrangement`' 9', the present authors carried out experiments to determine absolute structure of nitrohinokitiols. Another reason for the choice of vitro compounds is because, contrary to the case of bromo- and ehloro- hinokitiolsr~, the results of dipole moment measurements of dinitrohinokitiols and their converted compounds do not coincide with assumptions drawn by chemical procedures. It was the intention of the authors to determine the extent of the reliability of dipole moment measurements in hinokitiol derivatives by the present series of experiments. Five kinds of isomers of mononitrohinokitiols isolated to date"> were judged according to the conditions of their formation, stability (10) 26 T. Nozon, Y. KITAHARA,and K. DoI. [Vol. 26 of their crystalline compounds (addition products) with p-toluidine and aniline, presence of stereoisomers, their relationship to a-amino compound, and the ease or difficulty in the oxidation or reduction of m-cumic acid derivatives, their conversion products. As a result, it had been assumed that a-isomer (m.p. 56°) possessed the nitro group at o'-position, $-(m.p. 125°) and ry-(m.p. 155°) at o-, and b-(m.p. 158°) and possibly E-(m.p. 148°) at p-position. The probability of the position in a-isomer was pointed out by the result of its dipole measurement (6.19 D), but it also lacked positive proof. Consequently, the present authors began with the structural determination of a-mononitro-isohinokitiol (I)' ~, m.p. 182°, obtained by the alkali fusion of o-nitrohinokitiol (II), m. p.158°. The methyl ester (III), m.p. 930, of the amino compound (IV), m.p. 152°, ob- tained by the catalytic reduction of (I), yields to diazo reaction and substitution of its NH2 with OH, and gives methyl hydroxy-m-cumate (V), m.p. 101-102.5°. On the other hand, p-hydroxy-m-cumic acid (VI) (B : X = OH, R = H), m.p. 149-149.5°, was prepared through its p-methoxy compound> (VII) (B: X = CH:;O, R = H) from anisie acid (VIII), a compound possessing methoxyl in the p-position of the carboxyl group. Methylation of (VI) give a methyl ester of m.p. 103-103.5°, which was found by mixed fusion to be identical with (V). This result confirmed that a-mononitro-isohinokitiol (I) and ~-nitrohinokitiol (II) both possess nitro group in p-position, as assumed', and would correspond to formulae B(X = NO2) and A (X = NO2), respectively. Further nitration of a-mononitrohinokitiol (IX), m.p. 56°, yields a-dinitro compound (X), m.p. 155°, which is obtained by the direct dinitration of hinokitiol. As previously reported, (X) easily under- goes conversion by heating with alcohols or hydrous solvents, and yields dinitro-isohinokitiol (XI), m.p. 175°, or its ester. Furthermore,, reduction of one vitro group in (XI) and its subsequent deamination yields a compound coinciding with (I;), showing that one of the nitro groups in (XI) is in the p-position. In order to determine the position of the easily-reducible vitro group in (XI), i.e. the nitro group in a-compound (IX), (XI) was decarboxylated to dinitro-cumene (XIIa) and reduced by ammonium sulfide by which monoamino-mononitro- cumene (XIIIa), m.p. 49-50°, and its acetate, m.p. 111-112.5°, were obtainedz No. 10.] Substituent Positions in Hinokitiol Derivatives (I). (10) 27 Dinitro-c iimene (XIIb), obtained by the dinitration of cumene (E : X, = X, = R = H), was similarly reduced by ammonium sulfide as for (XIIa) by which 2-vitro-4-amino-cumene'°> (VIIIb), m.p. 50- 51°, (E : X, =NOD , X~=NHS , R=H), and its acetate, m.p. 113-113.5°, were obtained, which were proved identical with (XIIIa) and its acetate, respectively. To further confirm the positions of the two nitro groups in (XI) and (XII), sodium dichromate oxidation of (XII) was carried out by which, with a certain amount of resistance (XII) yielded crystalline dinitrobenzoic acid (XIV), m.p. 181-181.5°, and its methyl ester (XV), m.p. 69-70°. (XIV) and (XV) were found by mixed fusion to be identical with 2,4-dinitrobenzoic acid"', m.p. 181-181.5°, and its methyl ester'", m.p. 70°, respectively. Cons- equently dinitrohinokitiol (XI) is the o', p-dinitro compound (E : X, X2 = NO ; R = COOH), while a-mononitrohinokitiol (IX) is the o'- mononitro compound (C : X = NO). Finally, the structural determination was attempted on $-mono vitro-isohinokitiol'~ (XVI), m.p. 185-186°, a conversion product of the two stereoisomeric $-(XVIIa), m.p.125°, and 7-compound (XVIIb), m.p. 155°. As would be expected, the nitro group in (XVI) could not be reduced due to the great steric effect it receives. (XVI) also showed a certain amount of resistance to dichromate oxidation but finally yielded mononitro-isophthalic acid (XVIII) as its oxidation product. Its methyl ester (XIX), m.p. 129-130°, is identical with the known methyl ester of 2-nitrobenzene-1, 3,-dicarboxylic acid13 (H: X, = NOD; X2 = X;, = H ; R, = R~ = COOCH3). This compound was prepared from m-xylene through its 2-nitro compound (XX) (H : X, = NO.,; X2 = X, = H ; R, = R, = CH,) and was found-to be identical with (XIX). This has confirmed the identity of $-and y- mononitrohinokitiols (XVII) as the o-vitro compound (F : X = N02). Thus the structures of a-, $-, ~'- and -mononitrohinokitiols were unequivocally established and all were found to coincide with the assumptions~~ drawn by the authors. Up to the present, three isomeric dinitro compounds (a: m.p. 155°; $ : m.p. 160°; ry: m.p. 138°) have been obtained, of which a- and $- are stereoisomers possessing nitro groups at o'- and p-positions (D : X, = X,, = N02, X, H), so that the y-isomer must be o, o'-dinitro compound (D: X, = X:; = N02, X2 = H), although no confirmation of this point has yet been obtained. (10) 28 T. NozoE, Y. KITAHARA, and K. Doi. [Vol. 26, The authors have been designating these isomeric substitution products, a, 3, 7, etc., in the order of their isolation and identi- fication and, because there were no structural significance to these designations, they tended to lead, sometimes, confusion. Consequently, those compounds whose structures have been established will henceforth be designated, as in the 6-membered ring compounds, by the o, m, p-substituent positions on the tropolone nucleus. From the relative formation of p-nitrohinokitiol (A: X = NO.), a-monoamino, m.p. 131°, and its p-tolyiazo compound, m.p. 138°; a-monochloro-, m.p. 119.5°; a-monobromo-, m.p. 103°; y-iodo-, m.p. 98°, and a-cyano, m.p. 104°, compounds were all found to be the p-isomers (A: X = NHS,, p-CH;•C6ILN~ , C1, Br, I, CN). From the results of dipole moment measurements, dinitro- isohinokitiol (3.99 D) gives approximately identical value, as assumed from the standpoints of organic chemical investigations``, with that calculated for o,p- or o',p-dinitro compound. On the other hand, a-dinitrohinokitiol (4.36 D) gives a value entirely different from that calculated for o', p-dinitro compound (5.4 D) and more closer to those calculated for o, o'-dinitro compound (4.1 D), so that the assumption of substituent positions from its dipole moment was excluded in this instance. In this connection, one of the authors (Nozoe) considers it incorrect to judge entirely by the values cal- culated on the assumption that bond moment of the nitro group to be identical at o-, o'- and p-positions on the hinokitioF'>, because of the steric hindrance (J, and J~,) and hyperconjugation (K, and K,) with the isopropyl group in the m-position of the tropolone nucleus. Future studies must give final decision on this point. Experimental'4~. a-Amino•isohinokitiol or p-amino-rn•cumic acid (IV) : -0.56 g. of a-mononitro-isohinokitiol (I) is dissolved in 15 cc. of ethyl acetate and catalytically reduced at 40-45° with 0.03 g. of PtOr . absorption, 201 cc. (3 moles) in 4 hrs.
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