C₂₀GEのマウス経口投与による急性毒性試験を実施した結果, 5.00g/kgの投与によっても死亡例はみられず, C₂₀GEは極めて毒性の低い物質であると推察された。

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Generally, in liquid phase air oxidation, the naphthenic hydrocarbons with side chain are more readily oxidized and yield of lower fatty acids are greater than those without side chain but some exceptions are recongnized. The authors have investigated about the liquid phase air oxidation of methylcyclohexane (I) and isopropylcyclohexane (II). (I) and (II) were picked out as the representation of the naphthenic hydrocarbons having superior and inferior producibility of lower fatty acids respectively.
When (I) was oxidized for 23hrs. after induction period at 160°C using Mn catalyst with max. partial press. of oxygen at 4.5atm. (calculated for 0°C), 66% yield of formic acid plus acetic acid were obtained based on reacted hydrocarbon. In this case, the oxidation of the starting hydrocarbon was completed in 12hrs., after which oxidation of intermediates mainly proceeded.
In the oxidation of (II) a large part of acetone and considerable part of cyclohexane were obtained in the primary products. This indicates that the oxygen begins its selective attack on the tertiary carbon of side chain, then breaks the C-C bond between the side chain and cyclohexane ring. The poor yields of formic and acetic acid from (II) was explainable from the inferior producibility of formic and acetic acid by oxidation of these intermediates (acetone, cyclohexane, and cyclohexyl radical). The phenomenon of selective oxygen attack on the tertiary carbon of the side chain was also observed in the oxidation of sec-butylcyclohexane.

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ナタネ油の酸化の過程を考察する基礎実験としてエルシン酸メチルを空気酸化したとき生ずるの分析を行なった。本報の条件での酸化においては酸化時間20時間前後でエルシン酸メチルの性状変化がいちじるしいことをみい出した。また,この酸化過程で生成するをメチルエステルとしたのちガスクロマトグラフィーを行なった。メチルのガスクロマトグラフィーによる分離はポリエステルカラムが良好であった。既知メチルのガスクロマトグラフィーを行ない,エルシン酸メチルを酸化することによって,生じたの同定,および定量を行なった。酸化時間20時間前後より2C₁₃,2C₁₂等のの生成が起こり,酸化時間の長くなるにつれて,更に低鎖長のが生成する興味ある結果を得た。

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It has already been reported that Japan wax contains higher dibasic acids such as docosanedioic and eicosanedioic acids, but no detailed reports including the lower dibasic acids have been found yet.
The purpose of this investigation is to determine accurately the fatty acid and dibasic acid compositions of the wax by gas-liquid chromatography using a hydrogen flame ionization detector.
Gas chromatographic analyses were performed on a gas chromatograph of Shimadzu GC-1 B type equipped with a flame ionization detector. U-shaped stainless steel columns of 150cm×4mm i.d., and another 75cm×4mm i.d. for the specified analysis of higher dibasic acid dimethyl esters, were packed with 10% polyethyleneglycol adipate on Diabase B (Kotaki-seisakusho Co., Ltd.), 80-100 mesh. The flow rates of helium as the carrier gas, hydrogen and air for the detector were approx. 60ml/min, 40ml/min and 1.0l/min, respectively. The inlet heater was kept at 280°C, the column temperature was at 215°C for the analysis of fatty acid methyl esters and lower dibasic acid dimethyl esters, and at 220°C for the long-chain dibasic acid dimethyl esters.
As a result, different dibasic acids (C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₄, C₁₆, C₁₈, C₂₀ and C₂₂), various fatty acids (less than C₁₀, C₁₄, C₁₅, C₁₆, C₁₇ C₁₈, C₂₀ and C₂₂) and considerable amounts of unknown materials were found in the free acids responsible for the high acid value (21.5) of the wax.
In addition, the methyl esters, obtained by direct methanolysis of the wax and subsequent removal of the free acids, contained small amounts of C₁₄-, C₁₆-, and C₁₈- as well as C₂₀- and C₂₂- dibasic acids.
The thin-layer chromatography on silica gel was also applied to the analysis of the wax; namely, it was observed that the dibasic acids were separable from the fatty acids and other materials and that each constituent can be examined in detail.

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Polybasic fatty acids (PBFA) are now widely recognized as an important intermediate in various fields, because the carboxyl group can be easily converted to other versatile compounds such as glycidyls, anhydrides and hydrazides. In 1977, we established the full commercial scale technology to produce long-chain PBFA started from cyclohexanone in the presence of dienes or vinyl monomer by redox reactions. Since PBFA are readily available at reasonable cost, therefore, much efforts have been paid for their various uses.
This article reviws the recent trend of Japanese market on the utilization of PBFA.

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板紙抄造時の抄紙pHが7付近を示す抄紙系では，内添薬品の定着剤として使用されている硫酸バンドは失活しやすい。硫酸バンドの失活は紙力低下や濾水速度の低下，サイズ不良の原因となるが，硫酸バンドの効果不足を硫酸バンドの増添で補った場合，スケール発生や紙面欠点などのトラブルの原因となりやすい。一方で硫酸バンドは内添薬品の定着剤以外にも，抄紙工程の清浄化や脱水性の改善により操業性を高める効果があり，更にロジンサイズ剤のサイズ発現に必須であるため，使用量を低減することは難しい課題である。
本稿では，両イオン性ポリアクリルアミド（両性PAM）中のアニオン基に着目した検討を行った結果を紹介する。アニオン基として一塩基酸，，α-ヒドロキシ一塩基酸を比較したところ，α-ヒドロキシ一塩基酸を用いた場合に硫酸バンドの使用量を減らした抄紙条件における種々の課題を解決できる可能性がある両性PAMが得られることがわかった。

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When petroleum naphthas are oxidized with air for the purpose of preparing lower fatty acids, in most cases, crystalline matter which mainly consists of succinic acid are discovered when the aqueous layer of reaction products are concentrated. If pure succinic acid can be recovered from this crystal, the economical advantage should become very important. However, since this crystal includes various kinds of impurities, it was impossible to obtain satisfactory results by the known methods which have been applied for the purification of succinic acid.
After a number of experiments, the authors established a suitable process as outlined below for the purpose.
(1) At first, remove the benzene polycarboxylic acids as residue by means of hot water extraction at 100°C. (2) By solvent extraction, remove the materials which easily forms tarry matter when heated in the next dehydrating treatment. For the solvent, benzene, cyclohexane, etc. are desirable. (3) Then succinic acid in the crystal is dehydrated into succinic anhydride at 250°C. Ferrous succinate accelerates the reaction. (4) Separate succinic anhydride from adipic acid, etc. by vacuum distillation with 4 theoretical plates, reflux ratio of 3, and a operation pressure of 30∼50mmHg. (5) Remove the small quantities of impurities included in distillated succinic anhydride by solvent extraction.
According to these processes, succinic anhydride of at least 99.8% purity was obtained with a recovery yield of 80.5%. Succinic anhydride can be easily hydrated to succinic acid.

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Reaction of 1-methoxy-l-cyclohexylhydroperoxide with 1, 3-butadiene in the presence of iron (II) sulfate gave dimethyl 8, 12-icosadienedioate (6 b) (R=H) and dimethyl 8-vinyl-10-octadecenedioate (5 b) (R=H) in high yield and high selectivity.
When 1-methoxy-1-cyclopentyl (or cycloheptyl) hydroperoxide, in stead of 1-methoxy-1-cyclohexyl hydroperoxide, was used, the similar reaction proceeded in the presence of 1, 3-dienes to give the corresponding products (4 a and 4 c, 5 a and 5 c) in the moderated yields.

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不飽和ポリエステルの種類を決定するために,¹³C-NMRスペクトルを測定し各構成成分の化学シフトを確認した.標準化合物のスペクトルを得るために,種々の及びグリコール成分を用いて27種類の線状不飽和ポリエステルを合成し,分取用ゲル浸透クロマトグラフィーにより未反応物等を除去して精製した.得られた不飽和ポリエステルについて,IR,¹H-NMR,¹³C-NMRスペクトルを測定した.標準化合物の¹³C-NMRスペクトルより,構成する及びグリコール成分の化学シフトを整理した.その結果,各構成成分が2種類以上混在する場合,従来のIR,¹H-NMRのみでは識別が困難であった成分も¹³C-NMRスペクトルにより識別可能であることが分かった.

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The authors investigated the possibility of producing lower fatty acids by liquid phase air oxidation of pure naphthenic hydrocarbons, such as cyclopentane (I), methylcyclopentane (II), cyclohexane (III), methylcyclohexane (IV), ethylcyclohexane (V), o-(VI), m-(VII), p-dimethyl-cyclohexane (VIII), and isopropylcyclohexane (IX). Any reports on the application of these naphthenic hydrocarbons as raw materials for the manufacture of lower fatty acids have not been noted.
The oxidation was carried out under the following conditions:
A B
React. temp. 160°C 160°C
Catalyst None Manganese Naphthenate (0.01wt% as Metallic Mn)
React. time 6hr 6hr
Oxidizing agent Air Oxygen
Max partial press. of O₂ (calculated for 0°C) 4.5atm 4.5atm
It was found that the oxidizability and the compositions of the products were greatly affected by the structure of hydrocarbons.
The naphthenic hydrocarbons having methyl or ethyl side chain showed better oxidizabilities and higher yield of lower fatty acids than those without side chain. For instance, when (VIII) was oxidized under the above condition A, 96% conversion was obtained and total the yield of formic acid and acetic acid was 74.5% based on the reacted hydrocarbon. The yield of dibasic acids, however, were greater from naphthenic hydrocarbons without side chains than those with methyl or ethyl side chains. When the side chain is linked with tertiary carbon (IX) the oxidizability was very different from other cyclohexanes with side chain and gave low yield of lower fatty acids. It has been observed that the ratios of (acetic acid)/(formic acid) obtained from naphthenic hydrocarbons are affected by their molecular structures and increased according to the kind of side chain in the following order: (III)=(IX)<<(VIII)<(IV)<(V)<(VII)<(VI). Some considerations were made on these phenomena.

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Present research was carried out with the intention of finding the kinds of compounds formed by the action of 30% H₂O₂ on di-basic fatty acid esters.
The sample used was di-methyl ester of succinic-, adipic- and sebasic acid, and reacted without catalyst. By reacting 0.1mol of ester with 2.2mols of 30% H₂O₂ under the condition of 105° C and 30 hours, it was recognized that the various lower mono- and di-basic fatty acids and lower carbonyl compounds were produced.
Fixed quantity of carbon dioxide that produced by these reactions, and from these values, it was recognized that the lower esters were readily reactive than the higher homologue, and di-basic fatty acid esters were more readily oxidized than the mono-basic fatty acid esters.

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