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60. General Considerations on the Substitution Reactions O F Hinokitiol

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60. General Considerations on the Substitution Reactions O F Hinokitiol (9) 30 [Vol. 26, 60. General Considerations on the Substitution Reactions o f Hinokitiol. By Tetsuo NozoE. ChemicalInstitute, Faculty of Science, T~hokuUniversity. (Comm.by R. MAJIMA,M.J.A., Nov. 13, 1950.) The author'}, some time ago, discovered the presence of an enolic substance, C,OH,2O, in the essential oil of Chamaecyparis taiwanensis, Masamune et Suzuki, and named it hinokitiol. It existed in the oil mainly in a free state and partly as a ferric complex salt, hinokitin, m.p. 252°. From its oxidation and reduc- tion products, especially by the study of crystalline products ob- tained by H202-oxidation, the formula (I), corresponding to C10H1g0~, was adopted. However, as a result of extensive study by the author and his co-workers3~, hinokitiol, m, p. 52°, was found to be isopropylcycloheptatriene-2, 4, 6-ol-2-one-1 (II), corresponding to C,OH,~O2. From its remarkable characteristics, i.e. great stability in spite of its highly unsaturated structure, and the extreme aro- maticity, he assumed4~ its structure to be the resonance hybrid between formulae (ha) and (lib) by the formation of an intra- molecular hydrogen bond. As a result, the links between C-atom constituting the 7-membered ring, tends to acquire the double-bond character, and the molecule as a whole, takes a plane heptagone structure. This probably, is responsible for the aromaticity of hinokitiol, similar to- that of aromatic compounds of benzene series. The position of the isopropyl group was assumed to be at 4 or meta5~. Erdtman, Gripenberg and Anderson6), entirely independent of the foregoing research, studied the structure of 3 isomeric thuja- plicins, isolated from the heart wood of Thuja plicata, Ikon., and gave the same structure (III, R = i-CH) to its $-isomer, m.p. 52°. The coincidence of hinokitiol and , ?-thujaplicin was confirmed by Erdtman by the mixed fusion of the 2 substances. Moreover, Nozoe, et a1.7~, recently proved the structure of hinokitiol by a synthetic method. !o. 9.] General considerations on the Substitution Reactions. (9) 31 Prior to this, Dewars~, had proposed, that this structural frame (III, R = H) was present in the stipitatic acid and colchiceine mole- cules and named this hypothetical mother substance tropolone. Since 1948, Jeveral reported the existence of this tropolone nucleus in natural substances, and some related compounds have been synthesiz ed. The synthesis of tropolone itself was also independently carried out recently by Nozoe, et al.;, and by Doering and Knox. As to the exact structure of tropolone and hinokitiol, the author came to the conclusion'°~'2~ that, in order to explain the remarkable characteristics, it is essential to consider a system of resonance between a large number of structures that can be deviled into the following three non-ionic and ionic types (A, B and C). Both hinokitiol and tropolone possess amphoteric character, and, not only are they able to stabilize as an anion (D) in an alkaline medium to give salts or complex salts, but can also stabilize by accepting a proton in the presence of a strong acid to give a conjugate acid cation (E). From this point, they seem to comprise an unique system, which the author wishes to designate as a " tropoloid " system, quite different from that of the benzene series. (9) 32 T. NozoE. [Vol. 26, In order to examine this unique structure, the author enlisted the help of physical chemists, as well as experimental means of organic chemistry, and made determinations of infrared absorption spectra'2~, dipole moments' ~~and magnetic susceptibility'4~. By Kurita and Kubo'3~ the molecular orbital treatment was also carried out on tropolone, and the ~r-electron distribution, interatomic distances, free valence indices and dipole moments were calculated. It was shown that tropolone and its allied compounds possessed strong tenden- cy to form in tramolecular hydrogen bond, and that in a normal state, the type-B resonance was making chief contribution, the 6 ir-electrons revolving through the 7-membered ring and thereby allowing the ring C-atoms to have a positive formal charge. However, the fact that tropolone and its derivatives show fairly strong acid character and are easily substituted by various electrophilic reagents')10), shows that the contribution of type-C resonance cannot be dis- regarded. In the event of a collision with cationoid reagent, it must be assumed that the electromeric effect of the type-C would be in strong operation. It is remarkable to notice, in this connec- tion that, whereas hinokitiol is nitrated in glacial AcOH quite easily, or rather explosively if not controlled properly, it is quite unreactive in the presence of conc. H2SOa. It will be understood that the conjugate acid cation (E), formed in conc. H2SO4, cannot produce any center of high electron density. The fact that hinokitiol and its ethers possess a large exaltation of its molecular refraction3> also points to a great polarizability in these molecules. A great deal of interest is being paid now to the aromaticity of tropolone and related compounds. Although some crystalline Br- compounds were obtained from purpurogallin' and stipitatic acid'0~, formation of various substitution products of tropolone and its homologs have not been reported, with the exception of a mere mention of a crystalline bromo, and a red azo compounds of 7-thuja- plicin (p-isopropyltropolone). As a result of extensive investigation on the substitution reac- tion of hinokitiol, the author and his co-workers~~'°~, were able to isolate a large number of crystalline derivatives and examined their structures. These derivatives include : those of halogens-monochloro compds. (a: 118°, e : 48.5°, y : 4750); monobromo compels. (a: 560, $ : 41°, y :102°) ; monoiodo compds. (a: 49°, $ : oil, y : 98°); dichloro compds. (a: 130°, $:105°) ; dibromo compds. (a: 134°, $ : 96°) ; tri- chloro compd. (m.p. 64°) ; tribromo compd. (94°) and various mixed halogen compds. Nitroderivatives- mononitro compds. (a: 56°, $: 125° , :155° , :158° , s :148°) ; dinitro compds. (a: 155° , $: 159° , y :138° ); trinitro compd. (m.p.121°) ; and some chloronitro and bromonitro corn- No. 91 General Considerations on the Substitution Reactions. (9) 33 pounds. In addition, various kinds of azo (IX) and bromo-azo com- pounds were obtained, which easily undergo rearrangement by application of heat, especially in the presence of an acid, and form hinopurpurin&~ (X). Monoamino compds. (a :131°, ,&: 99°, y :121°) are obtained by the reduction of vitro and azo derivatives. Sulfona- tion of hinokitiol had not been realized for a long time but it has be- come possible to easily obtain various sulfonic acid derivatives. OH, CN and COOH derivatives have also been obtained quite recently. It has, therefore, become possible to obtain a majority of sub- stituents generally found in aromatic compounds. Above-mentioned derivatives are all true substitution products possessing intact tro- polone nucleus. It has now been confirmed thus, that, in spite of having an unsaturated, 7-membered ring structure, hinokitiol has an abnor- mally great aromaticity, since the partial reduction of its azo and nitro derivatives gives amino compounds with a reasonable yield, and moreover, the amino compounds give positive diazo reaction, similar to arylamines. It is Lure, however, that the compounds of tropoloid system have, in many respects, quite different characteristics from that of benzenoid system. Quite recently, Anderson and Nelson'>, communicated that, azulene (V), constitution of which is quite analogous to that of tropoloid compounds, was fairly susceptible to electrophilic reagents, and that they obtained nitro and diacetyl compounds which are assumed to be true substitution products. In tropolone nucleus, the position of double bonds, CO and OH groups, are assumed to be not fixed due to the resonance through the hydrogen bond. Since the position of the OH group may also change by the chelation with the adjacent electronegative groups (VII), confusion might arise by the ordinary numbering system (III) star- ting with the carbonyl group. For this reason, the author thinks that it would be more convenient to show the position of substi- tuents of the tropolone nucleus by the use of o-, m- and p- de- signations (III)) as employed in the benzenoid system, at least, as far as the monocyclic tropolone system is concerned. By this means the corresponding positions in the aromatic compounds (e.g. isohino- kitiol derivatives IV), formed by the rearrangement of a tropolone derivativ&>, can be shown by the same designations, and would also suggest the aromaticity of the tropolone derivatives. Prom the considerations of the electromeric effect of C - 0 bond (contribution of the type-C resonance), as well as from ir-electron distribution derived from molecular orbital treatment'3~, the positions in the hinokitiol molecule that are susceptible to electrophilic sub- stitution are assumed to be 3, 5 and 7 (or o, p and o') so that the number of isomers that are possible with one kind of substituent will be 3 each of mono- and di-substituents, and one kind of tri- (9) 34 T. NOZOE. [Vol. 26, substituted compound. The number of halogen derivatives obtain- ed to date, as described above, approximately coincide with this assumption. The kinds and yield of products obtained in the various sub- stitution of hinokitiol are complicated and varied, according to the conditions of reaction. The separation and purification of the products also are generally difficult, and an utmost care have to be exercised for repeated experiments. Because these are new type of compounds, unable to be linked with any known compounds, all the chemical methods possible were utilized in the determination of their structures, as well as physical methods, such as the me- asurement of dipole moments. In case an electronegative substituent is present in the o- or o'-position, the presence of tautomeric structure such as (VII), besides (VI), becomes possible, and in some case, resonance inhibition of the isopropyl group at m-position against o- and p- positions must also be considered, so that at present it would not do to put too much confidence in dipole mo- ments alone.
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