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A microorganism, strain KI 72 capable of utilizing e-aminocaproic acid cyclic dimer as sole carbon and nitrogen sources was isolated from sludge and identified as Achromobacter guttatus. This bacteria utilized 1% of the cyclic dimer in a day and was not inhibited by the higher concentration of the dimer. The growth rate was independent of the cyclic dimer concentration in the medium, but the maximum cell concentration increased with the increase of substrate concentration. The cell yield was 0.7 mg dry cell/mg e-aminocaproic acid cyclic dimer. Bacterial growth with the cyclic dimer as substrate was significantly stimulated by the addition of yeast extract. Ferric chloride was also stimulatory. Maximal growth was obtained in cultures incubated at pH 6 and at 33°C. Synthesized nylon oligomers, ranging from e-aminocaproic acid up to its linear hexamer, were found to be catabolized by this organism.

Meso-carbon microbeads were added in various pitches; coal-tar pitch, quinoline soluble coal-tar pitch (QS coal-tar pitch) and asphalt pitch, and these pitches were heat-treated at 400-430°C. A correlation between the microbeads added and the mesophase formed in pitch was investigated by using a polarized light microscope.The obtained results are follows;(1) In the case of addition of the microbeads of Type-M in QS coal-tar pitch, the growth of Type-M is observed but new mesophase is not formed in the pitch. For Type-P in QS coal-tar pitch, new mesophase spherules are formed in the pitch and their growth is predominant rather than the growth of Type-P . This is similar to the case of addition of Type-C and Type-M in asphalt pitch. From these results, it is considered that the growth of the added microbeads as well as the coalescence of new mesophase and the added microbeads requires similarity in molecular structure between pitch and meso-carbon microbeads.(2) In the case of addition of the microbeads of Type-C, Type-P and Type-M in coal-tar pitch containing metaphase, the microbeads added do not grow, and new mesophase spherules surrounded with metaphase are nucleated and grown. Thus the metaphase in pitch plays an important role in the formation of mesophase . In particular, the formation of mesophase spherules at the surface of metaphase in pitch is predominant than at the surface of microbeads themselves or of metaphase on Type-M. From these results, it is suggested that the metaphase in pitch has active site on itself for the formation of mesophase.(3) In the case of addition of Type-P in coal-tar pitch or addition of Type-C and Type-M in asphalt pitch, the microbeads added are dispersed in the pitch over the wide range, and coalesced with new mesophase formed in the pitch. It seems that coal-tar pitch is able to mix and melt homogeneously with asphalt pitch through the medium of mesophase.

An organism isolated from soil and identified as Arthrobacter sp. was studied for its squalene degradation. The degradation product from squalene, which accumulated in the culture broth, was isolated and identified as trans-geranylacetone by mass spectrometry, gas chromatography, infrared spectrometry, and nuclear magnetic resonance spectrometry. Addition of a high concentration of K 2 HPO 4 to the culture medium resulted in accumulation of fairly large amounts of carboxylic acids in addition to geranylacetone. These carboxylic acids were identified as isovaleric, β,β′-dimethylacrylic, geranic, and (+)-(R)-citronellic acids. Among these acids, α,β-saturated carboxylic acids were found to be predominant in quantity.

Pure (+)-trans-chrysanthemic acid was synthesized from (+)-⊿3-carene.Ozonolysis of (+)-⊿3-carene affords 2,2-dimethyl-3-(2-oxo-propyl)-cyclopropyl-acetaldehyde which was cyclized to (+)-2-acety1-6,6-dimethyl-bicyclo-[3,1,0]-2-hexene. The bicyclo compound was transformed into (+)-cis-homocaronic acid by ozonolysis followed by oxidation. Diester or anhydride of the acid and methyl magnesium iodide gave (-)-dihydrochrysanthemolactone which afforded finally (+)-trans-chrysanthemic acid via ethyl (-)cis-chrysanthemate.

In order to investigate ring structure of polycondensed aromatic hydrocarbons in binder pitches, solvent extracts of the pitches were analyzed by using a square wave polarography. Pitches used were five kinds, that is, straight coal-tar pitch, reformed coal-tar pitches and naphtha-tar pitch. Their pitches were fractionated by benzene and N, N-dimethylformamide (N, N-DMF). The reduction wave of the fractions (bezene soluble matter, and N, N-DMF soluble but benzene insoluble matter) were gained in N, N-DMF solution at the potential between 0 V and -2.35V vs Hg pool. Qualitative identification of reduction wave was carried out refering to the reduction potential of standard aromatic hydrocarbons.Results obtained were as follows, 1) All of polarograms for the benzene soluble matter showed the peak pattern having several reduction waves. Components in the straight and the reformed coal-tarpitches had aromatic ring structures such as shown in Table 3. But the reduction wave for the ring structure of anthracene, which may be included in coal-tra pitches, could not be detected. Naphtha-tar pitch consisted of aromatic ring structure such as tetracene, fluoranthene, pyrene and acenaphthene. The content of these components, however, was smaller than those in coal-tar pitches.2) For the N, N-DMF soluble but benzene insoluble matter, the polarograms showed the pattern having two reduction waves at about 0.5V and about-1.5V, and a broad line from about-0.5V to-1.5V. For this fraction, therefor, it is consi-dered that the identification of aromatic ring structure by using a square wave polaro-graphy is rather difficult.

The structure of aeruginoic acid which was isolated from the culture medium of P. aeruginosa was detremined and confirmed synthetically.

The chemical composition of binder pitches was examined by gas chromatography. Five kinds of pitches were used, that is, coar-tra straight pitch, three kinds of reformed binder pitches and naphtha-tar pitch.The volatile components were determined by programmed temperature gas chrom-atography. The column of 5% SE-30 (silicon gum) coated chromosorb W was employed over the temperature range 200-260°C at the heating rate of 4°C/min. From the results obtained, it is considered that there is a relation between total amounts of volatile components and softening point of the pitch, and pitch containing large amounts of lower boiling components such as naphthalene shows low softening point.Benzene insolubles in the pitch was examined by pyrolysis gas chromatography at temperature range 500-600°C. The components obtained were analyzed under the condition that the column of 5% SE-30 coated chromosob W was employed over the temperature range 100-260°C at the heating rate of 6°C/min. At the range of the above pyrolytic temperature, the components decomposed easily were those of composition which consist of the components bonded CH2 group.The components decomposed were classified four group, that is, 1) Ring number of polycondenced aromatic was 1 (benzene and its derivatives), 2) Ring number was 2 such as naphthalene, 3) Ring number was 3 such as anthracene and 4) Ring number was 4 or larger such as pyrene.The components decomposed at pyrolytic temperature 600°C were formed in larger quantities from benzene insolubles of naphtha-tar pitch comparing with those of coal-tar pitches. Main components obtained from benzene insolubles of naphtha-tar pitch were group 1 and 2, those from coal-tar pitches were 4. In the case of straight coal-tar pitch, however, the components of group 2 were formed in larger quantities comparing with those of reformed coal-tar pitches.

2-Methylpiperazino[1, 2-a]indole-6, 9-diones were synthesized as the analogues of mitomycin antibiotics. The compounds prepared from 2-carbethoxy-5-methoxyindole showed antibacterial activities.

(±)-Azetidine-2-carboxylic acid and 3-substituted-2-pyrrolidinones were synthesized from 2-pyrrolidinone via 3-bromo-2-methoxy-1-pyrroline (IIIa). The bromide (IIIa) was obtained by the bromination of 2-methoxy-l-pyrroline using NBS.

(±) -cis and trans-2,2-dimethyl-3- (2′-cyano-l′-propenyl) cyclopropane carboxylic acids and their optically active forms were synthesized starting from chrysanthemic acids via oximes of 2,2-dimethyl3- (2′-formyl-l′-propenyl) cyclopropane carboxylates. Their allethrolone esters were also prepared which showed insecticidal activity.

Quinoline-soluble coal-tar pitch, coal-tar pitch containing 3.4% free-carbon (quinolineinsoluble particles) and petroleum asphalt containing 5.4% sulphur were heat-treated for 120 min., 90 min. and 60 min. at 430°C respectively. Formation of mesophase spherules was observed by using a polarized-light microscope.The mesophase spherules were separated by solvent extraction from heat-treated pitches. The separated mesophase spherules were named meso-carbon microbeads and classified into type C, type M and type P according to above mentioned raw pitches. The shapes of meso-carbon microbeads were studied with a scanning electron microscope.The shapes of type C and type P can be divided into two classes, that is, the shapes of meso-carbon microbeads having larger size than about 5μm are approximately true spheres and those having smaller size than about 3μm are lemon-like spheroid. It is not obvious that the meso-carbon microbeads showing lemon-like shapes have the same lamellae structure as those larger than about 5μm, because the sensitive-tint technique can not be used for the meso-carbon microbeads smaller than about 3μm according to the resolving power of optical microscope.The shapes of type M are irregular, although their sizes are almost the same, and the free-carbon smaller than about 1μm are retained over the surface of mesophase.

(1) 火入醤油における3-デオキシペントソン(3-D-P)の存在について検討した結果,前報(1)で確認した3-デオキシグルコソン(3-D-G)に比して遙かに少量ではあるが,その存在を確認し得た. (2) 火入醤油にキシロースを添加(5%)して37°に保存すると,急速に3-D-Pが生成してくることを確認した. (3) 醤油のヘキソース並びにペントースを測定する簡便な方法として,オルシン-硫酸反応とBial反応とを用いた同時定量法を適用した. (4) 火入醤油を40°に保存または80°に加熱すると,着色度増加(470mμ)に伴ってヘキソースとペントースは減少するが, 3-D-Gは次第に増加して最高点に達した後ヘキソースの減少に平行して減少する.またキシロースを添加した火入醤油(5%)を40°に保存すると,同様に着色濃化に伴ってヘキソースとペントースは減少するが, 3-D-Gと3-D-Pは共に次第に増加して最高点に達した後それぞれヘキソース及びペントースの減少に平行して減少する,以上の事実から火入醤油の着色濃化現象において“アルドース→3-デオキシオソン類→着色物質”なる反応機構が存在することを推定した. (5) 火入醤油にグルコース及びキシロースを添加して空気と接触しない条件下で40°に保存すると,糖添加区はいずれも無添加区よりも着色度増加量が大きい.その際の糖減少量と着色増加量との関係から,少くともこの条件下では着色増加量の大部分は糖の消費によるものであること,また糖の単位減少量当りの着色増加への寄与はペントースの方がヘキソースよりもかなり大きいことを示した. (6) 火入醤油の着色濃化現象に対して空気(酸素)は促進作用を有し,空気との接触面積並びに接触時間が大きい程著しい.しかしながら空気と接触しないでも着色濃化は進行し,特にキシロースを添加(5%)した場合は非酸化的褐変反応が急速に進行する.

The 2,3-Dihydro-lH-pyrrolo[l,2-a]indole ring system was synthesised by the condensation reaction of toluquinone and 2-cyanomethylenepyrrolidine.

Pyrrolo[1,2-a]indoloquinones, IX and X, were synthesized and their antimicrobial activities as mitomycin analogues were bioassayed.

The behavior of meso-carbon microbeads in the boiling quinoline was investigated. The meso-carbon microbeads used were of three kinds; Type C, Type M and Type P. These were treated in quinoline at 238°C for 30 min. and the insoluble part was filtered out. This procedure was repeated five times. The amount of quinoline soluble part was measured and the structural characteristics of quinoline insoluble part were examined by IR spectroscopy, X-ray diffraction and scanning electron microscopy. The following results were obtained.(1) Almost all amount of quinoline soluble part in the three types of the meso-carbon microbeads was extracted after the first treatment. Among the three types, the amount of quinoline soluble part was highest in type P.(2) The characteristics of the quinoline insoluble part in the meso-carbon microbeads determined by IR and X-ray analyses were not altered from those in the non-treated microbeads. However, the meso-carbon microbeads were found to have several cracks after treatment in quinoline. The cracks developed in three or four directions starting from the point corresponding to the position of pole in the mesophase spherule proposed by Taylor et al. From these results, it was suggested that the formation of cracks in the microbeads by the treatment in quinoline is due to the release of internal strain of lamellae near the pole.

About sixty derivatives of mitomycin were synthesized from natural mito-mycins and subjected to antibacterial and antitumor tests. Some of them were more effective than mitomycin C. The structure-activity relationship of derivatives were also investigated.

Mitomycin A (C16H19O6N3) and mitomycin C (C15H18O5N4) are pigments which have the quinoid structure. When treated with aqueous ammonia, mitomycin A is converted to mitomycin C. Acid hydrolysis of mitomycin C gave three degradation products, namely, C14H15O5N4, C14H15O6N3 and C13H14O5N2. Acetylation with acetic anhydride and pyridine and methylation with methyl iodide gave monoacetyl and monomethyl derivatives of mitomycin C respectively, though diacetate of demethyl derivatives were obtained when boiled with acetic anhydride.

(±)-Azetidine-2-carboxylic acid and 3-substituted-2-pyrrolidinones were synthesized from 2-pyrrolidinone via 3-bromo-2-methoxy-1-pyrroline (IIIa). The bromide (IIIa) was obtained by the bromination of 2-methoxy-l-pyrroline using NBS.