A full account is given of the chemical behavior observed for 7, -dialkyladeninium salts (16). On treatment with boiling 1N aqueous NaOH for 60min, 16a, b, d, (X=I), 16 (X=Br), and 16 (X=ClO₄) rearranged to isomeric , 7-dialkyladenines (21a-) in 50-91% yields. Treatment of the salts with 0.5N aqueous Na₂CO₃ at room temperature for 30-90min or with Amberlite CG-400 (OH^-) in H₂O at room temperature gave the ring-opened derivatives a- (in the trans-formamide form) in 56-83% yields, and rate constants for the ring-opening reactions of 16a, b, d-g (X=ClO₄) and 16 (X=Br) leading to a-g were determined in H₂O at pH . and ionic strength 0.50 at 25°. Cyclization of a with NaH in AcNMe₂ at room temperature or with boiling 1N aqueous NaOH produced 21a in % or 72% yield, respectively.In solution, the trans-formamides seemed to transform slowly into the cis-formamides 23, attaining equilibria. The existence of such an equilibrium in D₂O or Me₂SO- at 25° or in H₂O at pH . and ionic strength 0.50 at 25° was kinetically confirmed in the case of a, and the mechanism of the rearrangement of 16 to 21 through is discussed on the basis of the above kinetic results and Deslongchamps' theory of stereoelectronic control. On treatment with NaBH₄ in MeOH at room temperature, 16a (X=I) furnished the 7, -dihydro derivative 28 (% yield), which slowly decomposed in H₂O at 60° to give a in 49% yield.The 7, -dialkyladeninium salts (16) were found to be obtainable from N'-alkoxy-1-alkyl-5-formamidoimidazole-4-carboxamidines () through an alternative synthetic route : Alkylations of with alkyl halides in HCONMe₂ in the absence of base, followed by hydrogenolysis of the N'-alkoxy group and cyclizatio (or vice versa) produced 16 in acceptable yields. In order to interpret the proton nuclear magnetic resonance spectrum of a, the 2-deuterated species 26 was also synthesized from 24 via 25 and 27.

抄録全体を表示

The Beckmann rearrangement of aliphatic ketone oximes, R(CHs)=NOH (R=Et (1); n-Pr (2); iso-Pr (3); iso-Bu (4)), with polyphosphoric acid (PPA), polyphosphate ester (PPE), and ester of phosphoric acid (2 P-5 R) was carried out and migratory ratios ((a)/(b) in eq. (1)) were determined, The results are shown in Fig.1, 2, and 3, respectively.
In Fig.1 and 2, the migratory ratios decrease with reaction time and nearly approach to the ratios of anti-alkyl form/syn-alkylform in benzene(A1) or DMSO(A2)except for (3) (See Table 1). From this fact, it has been found that PPA and PPE are inactive for isomerization of the oximes andanti-alkyl oximes rearrange faster than syn-alkyl ones. ln the case of (3), migratery ratios are smaller than Ai or A2. As acetonitrile is detected by GLC, it is presumed that fission has been occurred simultaneously with rearrangement in anti-alkyl oxime (eq. (3)). In the case of 2 P-5 R, all modes of the reaction arethe same as in above, except that the rate of fission is tnuch faster than that in PPA and PPE.
The reaction of anti-alkyl ketone oximes having a bulky grouphas been greatly influenced by the use of sterically demanding catalysts such asPPA, PPE, and 2 P-5 R.

抄録全体を表示

The advantages and disadvantages of using a back analysis of slope failures to evaluate soil shear strength are discussed. A methodology is presented herein that allows the implied level of reliability associated with soil shear strength parameters back calculated from slope failures to be estimated. A reliability approach is also used to estimate the probability of failure for a given limit equilibrium slope stability method, design factor of safety, and combination of back calculated Mohr-Coulomb shear strength parameters, ' and φ'. The methodology is illustrated using 39 landslides in the Orinda Formation in the San Francisco Bay area. The impact of additional case histories in the same geologic setting, i.., a larger data set, on the required design factor of safety for a given probability of failure is also investigated.

抄録全体を表示

Chemical properties of ergosta-4, , (14), -tetraen-3-one (1) were investigated. Though 1 is rather stable to acids or bases, it reacts easily with two moleculres of oxygen on irradiation with UV light to give , -epidioxy-14α-hydroperoxyergosta-4, 7, -trien-3-one (2), which is transformed successively to , 7α;, -diepoxy-14α-hydroperoxyergosta-4, -dien-3-one (3) and 14α-hydroperoxy--hydroxyergosta-4, 7, -triene-3, -dione (4) under these reaction conditions.

抄録全体を表示

Four new sterols, 5α, -epoxy-(, 24R)-ergosta-(14), -diene-3β, 7β-diol (1), (, 24R)-ergosta-, -diene-3β, 5α, , 7α-tetrol (2), (, 24R)-ergosta-7, (11), -triene-3β, 5α, -triol (3) and 3β, 5α, -trihydroxy-(, 24R)-ergost--en-7-one (4), have been isolated from the fruit bodies of Grifola frondosa (FR.) S. . GRAY (Polyporaceae)together with fourteen known ones (5-18), of which two (5 and ) are reported for the first time from a natural source. The structures of these compounds were elucidated on the basis of spectral data.

抄録全体を表示

Six new cembranoids sarcophytol P (3), R (4), S (5), K (), (11), and T (13) were isolated from the soft coral Sarcophyton glaucum. Sarcophytol P (3) was shown to be the 20-hydroxy derivative of the major component sarcophytol A (1), and afforded the cyclization product in CHCl_3 at room temperature, in a same way as in 1. Sarcophytols R (4) and S (5) were correlated to 1, by conversion of its 7R,R and 7S,S epoxide derivatives. Sarcophytol K() was a 13, 14-dihydroxycembranoid having a 1,3Z-diene moiety. The absolute configuration of and its 1Z,3- and 1Z,3Z-isomers sarcophytol B (2) and J (10) were determined by circular dichroism study of their bis-p-dimethylaminobenzoate derivatives. Sarcophytols (11) and T (13) were 1- and 1,3Z-isomers of 1. Compound 11 showed characteristic broadening of the ^1H-NMR chemical shifts, due to the restricted conformational interconversion. Using the three cembranoids sarcophytols (11, 1,3), N (15, 1Z,3Z) and T (13,1,3Z), spontaneous autoxidation-cyclization, in CHCl_3,was examined, in order to compare the stereochemical course of the reaction with that of 1 (1Z,3), which affords trans-fused bicyclo[.3.0]tetradecene systems. The 1,3Z-isomer 13 gave the same cyclization product 18, as in the reaction of 1, even though it is isomeric at -1,3. The 1Z,3Z isomer 15 gave 19, in consequence of the reversed geometry at -3 of 15. The 1,3-isomer (11) gave the bicyclic product , having an antipodal fusion as compared with 19. This was confirmed by PCC oxidation of 19 and , giving enantiomeric ketones 23 and 24 respectively. The 1(14)-epoxide 26 was shown to be the immediate precursor of , and acounted for the inversion of the geometry at -1 of the cyclization product. Compound 26 is isomeric with the epoxide 17 derived from 1. The epoxide 17 is the postulated precursor in the conversion of 13 to 18. It is noteworthy that the mode of antipodal fusion of the cyclopentane rings, in 18 and , was controlled by the chirality of the epoxy rings. The -14 hydroxyl group participates in the transannular cyclization, but was found not to be the requisite functional group for the reaction. Similar treatment of cembrene (30), the parent hydrocarbon of 1, also reacted in CHCl_3 giving the bicyclic product 32.

抄録全体を表示

Ten furostanol saponins were isolated as five pairs of 25R and 25S epimers from the fresh rhizomes of Polygonatum kingianum. Seven of them were identified as new compounds, (25S)-kingianoside D (2), (25S)-kingiano-side (4), (25R,)-hydroxylwattinoside (5), kingianoside (7), (25S)-kingianoside (), kingianoside () and (25S)-kingianoside (10), together with three known saponins, kingianoside (1), kingianoside D (3), and -hydroxylwattinoside (). The structures of the new saponins were determinded by detailed analysis of their 1D and 2D NMR spectra, and by comparison of the spectral data with those reported.

抄録全体を表示

　わが国では，近年，豪雨災害が多くなり，都市域が冠水する事象が多発している．浸水地域に工場などの危険物質を取り扱う施設があれば，その流出が懸念され，浸水地域に長期間の悪影響を及ぼすものと考えられる．すなわち，洪水による危険物質の流出に対する対策の検討をすることは，洪水災害からの復旧・復興だけでなく，減災対策を立てる上で役に立つ．本研究では，まず過去の国内外で発生した豪雨災害に伴う危険物質の流出事例をレビューした．そして，わが国における水害発生時の危険物質の流出リスクについて，その可能性がある事業所（工場），農家，一般家屋に分類して調査を行った．さらに，危険物質が流出した場合の拡散の様子について，平面2次元拡散方程式の解析解を用いて簡易推算した．これらを踏まえて，水害による危険物質の流出対策について考察を行い，二，三の提案を行った．

抄録全体を表示

　急傾斜地崩壊防止工事で床掘りを伴った待受け擁壁設置での対策工事において，コンクリート打設の際に残存型枠を使用した．残存型枠は，一般型枠のように足場の設置や型枠の撤去が無いため，工事工期の短縮，作業性または工事費の縮減に対して有効であるとされている．また，施工中の安全面においても崩壊危険リスクが高い擁壁背面（斜面側）での作業工程が減少するので，このような工事では安全性の向上も期待される．本論文は崩壊防止擁壁施工時の床掘りや急勾配掘削を行った斜面近傍で行う作業で残存型枠を使用したより安全となる施工方法についてその有効性について調査・検討を行った．

抄録全体を表示

　近年，地域公共交通における運転手不足が深刻化しており，運転手の不足に伴う労働負担の増大が，運転手の離職を促し，更なる運転手不足を招く悪循環に陥っている．

　そこで本研究では，運転手が充足定員の50%しか確保できておらず，運転手の労働負担増大と，路線バスのサービス低下に直面する実際の地域を対象として，バス運転手の労働時間を制約条件として，運転手の労働負担を軽減できる公共交通の運行計画を検討した．

　検討は，バス運転手の労働時間軽減と，最低限必要と考えられる公共交通のサービスレベルを両立できる複数のシナリオを作成し，シナリオ分析及び重回帰分析を行った．

　本研究の結果，路線バスの運行に従事するバス運転手の増員のみを行うよりも，バス運転手の増員と一部バス路線の撤退を組み合わせた方が，バス運転手の労働負担の軽減に効果が見られることが明らかとなった．

抄録全体を表示

　愛媛県宇和島市吉田町では，平成30年7月豪雨における被災者に対する生活再建支援が進められている．被災者の生活再建を進めていく上では，被災者の孤立リスクを軽減すると共に，彼らが自分達の暮らしを肯定的に評価し，日々の暮らしに幸せを感じられるかどうかが課題となる．本研究では，宇和島市の生活再建支援プログラムの内容や課題を踏まえて，吉田町の被災者350世帯を対象に，被災者の孤立リスクや生活満足度（主観的幸福感）を把握すると共に，その規定要因を検討した．その結果，被災者の生活満足度は，ソーシャルサポート意識や民間支援との間に強い関連性が認められた．また，被災後の移転者と非移転者の間で孤立リスクや生活満足度の規定要因に顕著な差異が認められた．これらの結果より，移転者には新しい環境において孤立を感じないように配慮することの重要性が示唆された．

抄録全体を表示

　大規模災害等では，災害対策本部の運営を中心に，ICS（Incident Command System）における目標管理型災害対応の観点から「定期的な対応計画の作成」「目標の設定と定期的な業務のチェック・改善」の導入が進んでいる．しかし，もう一つの重要な柱である「権限委譲」に関しては様々な事例報告があるものの，その実態に関する議論が不十分である．本稿では，和歌山県における災害事例を対象に，県行政の出先機関への調査等から災害現場における権限委譲の実態と課題を明らかにする．また，権限委譲の課題解決には，地域ステークホルダーと県行政機関との関わり，あるいは現地指揮官による状況判断や意思決定過程を検討する必要がある．そのためには「組織論」によるアプローチのみならず，「組織間関係論」さらには「組織行動論」としてとらえ議論する必要があることを提示する．

抄録全体を表示