We have investigated the interaction of the dissolved water and oxygen in methyl decanoate, decanoic acid, and 1-decanol, which were chosen as model compounds of fatty oils and their derivatives. On the bases of the time of oxygen saturation in water, the saturation time in decanoic acid containing water (6112350 ppm) was shorter than in water (0.650.88 times), but in 1-decanol (19130794 ppm H2O) it was longer than that in water (1.51.9 times). In methyl decanoate (452789 ppm H2O), it was changed from 0.75 to 2.1 times of the saturation time in water. The interaction of the dissolved water and oxygen was small under the influence of the formation of hydrogen bonds between hydroxyl and carboxyl groups and the dissolved water. While the water dissolved in methyl decanoate did not form hydrogen bonds and filled up the intermolecular free volume, it is considered that the dissolving rate of oxygen may greatly change with the amount of dissolved water. Compared the dissolution time of oxygen with the degassing time of oxygen in above three compounds containing water, the latter was longer than the former. From these results, it is shown that the dissolved water interacts with the dissolved oxygen.
Copolymerization of vinyl acetate with maleic anhydride in 1-dodecanethiol, carbon tetrachloride or benzene in the presence of α, α'-azobisisobutyronitrile as an initiator afforded cotelamer LS, cotelomer C, end copolymer P, respectively, as shown below. _??_ R=C12H25S, W=H (LS-series), R=CCl3, W=CI (C-series) and R, W : unknown (P-series) These cotelomers and copolymers were treated with aqueous sodium hydroxide, ammonia or n-dodecylamine to give corresponding cotelomeric or copolymeric surfactants having OH, C02Na, CO2Na, or CONHC12H25 functions : _??_ c=d=0 (S-derivatives), c≠0, d=0 (A-derivatives) and c≠0, d≠0 (D-derivatives) Their structures were deduced from the molecular weight measurements, elemental analyses, and IR spectra. They showed surface active properties as follows. 1) The surface tension of LS-S as well as LS-A were 4043 dyn/cm at pH 1. 2) The cmc of LS-S was correlated with the degree of polymerization (Pn) by cmc=0.16 Pn -0.4 (at Pn=9.828.6). 3) LS-D had cmc of 10-2 wt% in the neutral pH range. 4) LS-S showed CaCO3 dispersion ability of ca. 75% at the concentration of 10-3 wt%. 5) S and A derivatives in the LS, C and P series formed water insoluble complexes with Hg2+ and Fe3+ at pH 1 as well as with Pb2+ at pH 3, while D-derivatives formed water insoluble complexes at pH 3 with various metal ions except Fe3+.
The thermal isomerization of myrcene (1), dihydramyrcene (2), and alloacimene (3) in the presence of ZnCl2-KCl-NaCl fused salts (Chlorate fused salts) or NaNO2-NaNO3-KNO3 fused salts (Nitrate fused salts) was carried out under different temperatures and the salt effect of the products was studied. The results obtained are as follows : In the Chlorate fused salts, 1, 4-p-menthadiene (4) and 1, 8-p-menthadiene (5) were obtained as the two main products from (1) and (3). In the Nitrate fused salts, 2, 4 (8) -p-menthadiene (7) (product ratio 60%) was obtained from (1). α- and β-Pyronenes (14) and (16) were obtained as the two main products from (3). Under particular conditions, the (14) and (16) ratio was 30 : 47. In both fused salts, α- and β-cyclodihydromyrcenes (11) and (12) were obtained as two main products from (2) at the highest conversion (product ratio 62%, 45%) among the isomerization products.
The homogeneous mixtures of sesquiterpene hydrocarbons as β-caryophyllene (1), humulene (2), β-and γ-elemenes [(3) and (4)], α- and β-selinenes [(5) and (6)], thujopsene (7), longifolene (8) or α cedrene (9), and acetic acid were passed through in glass tube packed with cation exchange resin at room temperature. The hydration of (1) took place to give β-caryophyllene alcohol (10), dihydroneocloven-4β-ol, and dihydrocloven-9β-ol (12), along with isomerization products, neoclovene (1a) and clovene (1b). Humulol (13), was obtained by hydration of (2) in high selectivity. Only elemol (14) was obtained from (3) and (4). A similar hydration of (5) and (6) was found to afford three products, γ-eudesmol (15), α-eudesmol (16), and β-eudesmol (17). And also, the hydration of (7) gave widdrol (18), along with widdrene (7a), isowiddrene (7b), and β-chamigrene (7c). Compound (8) or (9) has no reaction to an offer. * Stadies on the Hydration of Terpenes. XVI.
The title compounds were prepared from the dimer of 3-buten-2-one, 3-methylene-2, 6-heptanedione (1). The reaction of (1) with methylmagnesium chloride in THF gave 2, 6-dimethyl-3-methylene-2, 6-heptanediol (2) in 95% yield. When (2) were treated with various acidic catalysts, it was dehydrated to the corresponding terpene compounds. For example, 2, 2, 6, 6-tetramethyl-3-methylene tetrahydropyrane (3) was obtained by dehydration of (2) with p-toluenesulfonic acid. By treating by (2) with acetic anhydride, 1, 1, 5-trimethyl-4-methylene-5-hexenyl acetate (6) as a new terpene compound and 5-acetoxy-2-isopropylidene-5-methylhexyl acetate (7) were obtained. Isolavandulol acetates (9) and (10) were obtained from diacetate (7).