Masashi Sumimoto

The structure and absolute configuration of verticillol, a macrocyclic diterpene alcohol from the wood of sciadopitys verticillata sieb. et zucc. (taxodiaceae)

Abstract The structure of verticillol diepoxide 4 has been established by direct single crystal X-ray analysis. The structure of verticillol 5 follows from the chemical correlation to the diepoxide 4 as well as from NMR-LIS studies on verticillol which also provide evidence for the conformation of this alcohol. The absolute configuration of verticillol 5 has been assigned on the basis of CD data for the verticillol norketodiepoxide 6a.

Sesquiterpene alcohols from Cryptomeria japonica and C. fortunei leaf oil

Abstract 4β-Hydroxygermacra-1(10),5-diene, thujopsan-2α,-ol and hedycaryol were found in the leaf oil of Cryptomeria japonica obtained by hexane extraction. Both the first and last were present in all races of C. japonica native in Kyushu main island, but thujopsan-2α-ol was found in about one-third and not found in C. fortunei so far examined. Moreover, some C. fortunei lacked 4β-hydroxygermacra-1(10),5-diene. On the other hand some contained only this as sesquiterpene alcohol. When the leaves were steam-distilled, 4β-hydroxygermacra-1(10),5-diene isomerized to α-cadinol and hedycaryol isomerized to elemol and eudesmols. Thujopsan-2α-ol was synthesized from mayurone.

The Termiticidal Substances from the Wood ofChamaecyparis pisiferaD. Don

The termiticidal activity of different fractions of the essential oil of Sawara wood (Chamaecyparis pisifera D. Don) were persued. The neutral fraction possessing the whole activity of original wood chromatographed on alumina column followed by preparative T. L. C. and G. L. C. finally yielded strongly active B2_3, B3_35 B2_4 and B3_4 fractions. Chamaecynone, a major component of B2_3 and B3_3 fractions, and isochamaecynone, one of the main components of B2_4 and B3_4 fractions possess marvelous termiticidal activity, however, the presence of other derivatives of Chamaecynone and their high activities are also expected. Thus the activity of Sawara wood (Ch. pisifera) is due to these minor components which are new types of termiticides having high volatility and acting as contact insecticides.

Mechanochemistry of Lignin - V. An Intensive Chromophore in Mechanical Pulps Bleached with Alkaline Hydrogen Peroxide

An intensive quinoid chromophore (IV-Q) was formed under daylight Irradiation of a hydroquinone derivative (IV—H), which was obtained by alkaline peroxide bleaching of a mechanochemical reaction product (IV—S) obtained from a phenylcoumaran lignin model. Chromophore IV—Q shows an absorption maximum at 460 nm in methanol and at 500 nm when impregnated in filter paper, both accompanied with a broad absorption in the ränge of 400—700 nm. Under Irradiation, chromophore IV—Q was bleached quickly with 1-thioglycerol to yield the corresponding hydroquinone (IV—H) and a Michaeltype addition product (IV-HT).The latter compounds were converted, however, readily into the corresponding quinones (IV-Q and IV-QT, respectively) in the absence of 1-thioglycerol. Based on these results, formation of a quinoid chromophore (11) was proposed in connection with the behavior of the lignin residue in peroxide bleached mechanical pulps.

Heartwood constituents of sciadopitys verticillata sieb. et zucc.-II. The structure of methyl sciadopate

Abstract The structure (II) is proposed for methyl sciadopate, a new diterpenoid ester, which has been correlated to agathic acid.

Mechanochemistry of Lignin. XVII. Factors Influencing Mechanochemical Reactions of Veratrylglycerol-β-syringaldehyde Ether

Mechanochemical reactions of a lignin model compound, veratrylglycerol-ß-syringaldehyde ether I, were investigated using ball mills and a refiner under various conditions. As a result of the mechanical treatment, the model compound was converted to syringaldehyde 3, 3,5-dimethoxy-/?-hydroquinone 4, 3,5-dimethoxy-p-benzoquinone 5, veratrylalcohol 7 and five other compounds to a large extent. The reactions proceeded mainly via radical mechanisms. More homolytic cleavage of Ca-Cß or Cß-O bonds in compound I took place, and more oxygen-containing species such äs -C^H and -OH radicals were generated during millings at higher treatment temperature. The presence of toluene and methanol in the mechanical treatments greatly reduced the formation of the products, probably because the solvents scavenge -OH radicals in reaction fields.

Further attractasnts for the scolytid beetle, Taenoglyptes fulvus

Abstract In field tests, mentha-1,8-dien-4-ol, a major oxidation product of d -limonene with selenium dioxide, greatly increased activity for the scolytid beetle, Taenoglyptes fulvus (Cryphalus fulvus auct. ). The attractant, however, does not seem to be contained in neutral host volatiles from fresh phloem of Pinus densiflora , and this suggests that it may be either a sort of pheromone of beetle origin or, if not, simply a mimic. Further detections of the oxidation products of pinenes, i.e. pinocarvone, trans-pinocarveol, and verbenone in the host volatiles, in addition to those of myrtenal and myrtenol are also described.

Comparative Studies on the Mechanochemistry of Guaiacylglycerol- and Veratrylglycerol- β -Guaiacyl Ether

Abstract Treatments of guaiacylglycerol- and veratrylglycerol-β-guaiacyl ether [I] and [II] with CBM, VBM and laboratory refiner furnished α-(2-methoxyphenoxy)-β-hydroxypropioguaiacone 1 as the major product in addition to a few small compounds 2-7 in relatively low yields. In addition, 5,5′-condensation reaction of compound [I] gave compounds 8 9, and 10. Alternatively, Cα-Cβ splitting reaction of veratrylglycerol-β-guaiacyl ether [II] occurrsby the mechanical treatment to give a number of products (6,11-14, and 15). Compounds [II] also formed p-carbonyl phenol 1 and products 2 4, and 7 by an alternate route. For comparison, mechanical treatments of vanillyT alcohol [III],α-methyl vanillyl alcohol [IV], and veratryl alcohol [V] were made with a ceramic ball mill (CBM), vibration ball mill (VBM), respectively. Former two gave vanillin 15 and acetovanillone 16, but no product was found from veratryl alcohol [V].

Generation of Oxygen-Containing Radicals in the Aqueous Media of Mechanical Pulping

Abstract Mechanical treatments of veratrylglycerol-β-syringaldehyde ether (M) were conducted with a ceramic ball mill or a vibration ball mill in the presence of water and n-paraffin alcohols which were used as ·OH scavengers. Addition of 1% each of the alcohols to the milling process of Compound (M) greatly decreased the yields of the products, e.g. veratryl alcohol 2, vanillin 3, syringaldehyde 4, 3,5-dimethoxy-p-benzoquinone 5, 3,5-dimethoxy-p-hydroquinone 6 and others. Another addition of n-paraffin alcohols to aqueous media during the millings also significantly reduced the concentration of H2O2. When phthalic hydrazide (P) was treated in the mills in the aqueous media, triacetoxyphthalazine (1A), 3-acetoxyphthalic acid (2A) and other products were separated from the acetates of the reaction mixtures. Results mentioned above disclosed the generation of ·O2H, ·OH, and ·H in the aqueous media during the mechanical treatments.

Mechanochemistry of Syringylglycerol-β-Guaiacyl Ether and Its Similarity to the Conventional Bleaching of Mechanical Pulps

Abstract Syringylalcohol (1), α-methyl syringylalcohol (2), 3, 4, 5-trime-thoxyphenyl methylcarbinol (3) were dispersed onto filter paper pulp or linter pulp, and treated, respectively, with a ceramic ball mill (CBM) or a vibration ball mill (VBM-1 or -2) under air for 1h. Mechanical treatment of VBM-2, having the more rigid surface of linter pulp, furnished the p-carbonylphenols (5), (6), and 3, 5-dimethoxy-p-benzoquinone (7). Mechanical treatments of syringylgl-ycerol-β-guaiacyl ether (4) with CBM, VBM, and a laboratory refiner provided α-(2-methoxyphenoxy)-β-hydroxypropiosyringone (8) in the highest yield and a less yield of p-quinone derivative (7) and others as shown in TABLE 2 and FIGURE 3. When treated the resultant mixture with alkaline H202, the chromophore (III) can be decomposed, but remarkable amounts of the leucochromophre (IV) are produced as shown in FIGURE 4.