著者
稲木 良昭
出版者
社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.51, no.3, pp.188-202, 1993-03-01 (Released:2009-11-16)
参考文献数
31
被引用文献数
6 7

Pyrimidine derivatives were found to be applicable to photoresists for microelectronics. This paper deals with synthesis and photochemistry of pyrimidine derivatives, and application to photoresists. Intermolecular photodimerization of pyrimidine bases in the side chains of various polymeric and dimeric compounds upon irradiation of UV light (270 nm) led to photocrosslinking of the polymer chains or photopolymerization of the dimeric compounds. These materials can be used as deep-UV negative type photoresists. On the other hand, the polymers containing thymine photodimers in the main chain underwent dissociation of the thymine photodimers upon irradiation to UV light (250 nm), leading to breakage of the polymer chains. These polymers could be used as positive type photoresists and high resolution (0.3μm) was demonstrated. Tautomerism of pyrimidine was also applied to a chemical amplification photoresist system. Polymers containing 2, 4-dialkoxypyrimidine derivatives that is an enol form of uracil were high sensitive deep-UV, and EB chemical amplification resists.
著者
的場 勝英 利根 斉 新浜 光一 後藤 文孝 坂 雅之 南川 純一
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.57, no.5, pp.407-414, 1999-05-01 (Released:2009-11-16)
参考文献数
3
被引用文献数
1 6

An efficient and practical synthetic route to OPC-15161 (1), a novel inhibitor of superoxide anion generation, is described. Intensive survey on pyrazine ring manipulation has led to the development of multi-kilo synthetic pathway, in which beneficial use of a nitrogen protecting group is the key to the problematic cyclization and O-methylation process, both being carried out in one-pot operation. Thus, the synthesis proceeds in 40% overall yield in four steps from tryptophan methyl ester with simple operation and without chromatographic purification, which also opens a general route for the preparation of related 5-alkoxypyrazin-2 (1H) -one 4-oxide such as emeheterone.
著者
松原 義治 山賀 谷一郎 辻川 康二 若林 昭二
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.28, no.8, pp.849-852, 1970-08-01 (Released:2009-11-16)

従来合成されたアセタールは低分子量のアルコキシ基に限られているので, さらに高い保留効果を期待して大きいアルコキシ基を持ったアセタールとその誘導体の合成を行なった。シトロネラール (1) を母体としてシトロネロール (2), ゲラニオール (3) を用いてシトロネリノレ (4), ゲラニル (6) アセタール, あるいは (2), (3) の混合アセタール (5) を合成し, さらに (4), (5), (6) の飽和アセタール (8), (8) から誘導されるアルキノレビニルエーテル (10), その飽和エーテル (11), を合成した。 (4), (5), (6) は硫酸, リン酸, ギ酸水溶液などで冷却下, 分解するともとの (1), (2), (3) が, (8) からはジヒドロシトロネロール (7) が得られる。また (4), (5), (6), (8) を水素で分解すると (7) が得られる。(4), (5), (6), (8) はいずれもヒドロキシシトロネラールようのおだやかな花香を持ち, bp200℃/1mmHg以上で, 保留効果の優れた皮ふ刺激のない安定な香料として有用と思われる。
著者
尾島 巖 稲葉 伸一
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.36, no.7, pp.610-615, 1978-07-01 (Released:2010-01-22)
参考文献数
38
被引用文献数
4 4

Ketene silyl acetals have been developed as new versatile reagents for organic synthesis. The reactions of ketene silyl acetal with acid halides, carbonyl compounds, Schiff bases, and heterocummulenes and summarized. Oxidative coupling, oxidation and Mannich reaction of these reagents, and, an application of Claisen-type rearrangement of these reagents to the total synthesis of natural products are also described.
著者
井上 宗宣
出版者
社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.75, no.4, pp.310-319, 2017-04-01 (Released:2017-04-28)
参考文献数
76

The introduction of fluorine-containing carbon functional groups into organic compounds is one of the key processes to synthesize biological valuable organofluorine compounds. While the reaction of organolithium, magnesium and zinc reagents with appropriate carbon electrophiles is reliable method to form carbon-carbon bonds, there were few reports concerning the reaction of these organometallic reagents with electrophilic fluoroalkylating reagents. Recently, we have developed several fluoroalkylations using these organometallic reagents and electrophilic fluoroalkylating reagents. In this paper, we account the fluoroalkylation of aromatic lithium, magnesium, and zinc reagents including our developed bromodifluoromethylation of aryl Grignard reagents with CF2Br2 and dibromofluoromethylation of aryl Grignard reagents with CF2Br2 in the presence of LiBr. In addition, the (ethoxycarbonyl)difluoromethylation of arylzinc reagents with ethyl bromodifluoroacetate in the presence of cobalt catalysts is also discussed.
著者
田中 正一
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.60, no.2, pp.125-136, 2002-02-01 (Released:2009-11-13)
参考文献数
55
被引用文献数
15 19

Replacement of α-hydrogen atom of α-amino acids with alkyl substituents affords α, α-disubstituted α-amino acids, which are non-proteinogenic amino acids. This kind of modification changes the conformational freedom of peptides containing such residues. 2-Aminoisobutyric acid (dimethylglycine, Aib) is a natural product, isolated as a component of peptaibol antibiotics, and is widely used among peptide chemists for the construction of helical secondary structure. Contrary to 310-helical structure of Aib homopeptides, the conformation of homopeptides prepared from diethylglycine or dipropylglycine is a fully planar C5-conformation. Besides achiral α, α-disubstituted α-amino acids, the conformation of homopeptides prepared from chiral α-methylated or α-ethylated α, α-disubstituted α-amino acids was recently reported. The conformation of homopeptides prepared from chiral α-methylated α, α-disubstituted amino acids is the 310-helical structure and the screw sense of helicity (P) or (M) depends on the chirality of quaternary carbon center of amino acids, while that of α-ethylated α, α-disubstituted amino acids is the fully planar C5-conformation. The application of α, α-disubstituted α-amino acids for the design of biologically active peptides and catalytic peptides is also described.
著者
新井 和孝
出版者
社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.44, no.6, pp.486-498, 1986
被引用文献数
8

In recent years, synthetic method by the combination of isomerization and crystallization is studied intensively, especially in the practical optical resolution. In this paper, this isomerization-crystallization method is introduced from a point of view of practical organic synthesis. A number of examples of this isomerization-crystallization method in optical resolution, many of which were often reported as the example of second-order asymmetric transformation phenomena, are classified into following two groups, and reviewed.<BR>(1) Epimerization-crystallization method.<BR>(2) Racemization-preferential crystallization method.<BR>The potentialities and difficulities of each method are also discussed. The compounds resolved by this methods are &alpha;-amino acid derivatives, cyanohydrin derivatives, &alpha;-aromatic carboxylic acid esters, and so on.
著者
早川 謙二
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.45, no.1, pp.60-70, 1987-01-01 (Released:2009-11-13)
参考文献数
41
被引用文献数
2 3

New approaches to the heterocyclic syntheses through pericyclic reactions are presented in three sections.(1) The utility of (phenylsulfonyl) propadiene (1) as an allenic dienophile and/or electrophile was revealed by its facile intermolecular cycloaddition reactions with electron-rich dienes, tropone, azaheptafulvenes, and thebaine derivatives, which afforded various heterocyclic compounds including some novel ring systems. (2) trans-4- (Phenylsulfinyl) -3-buten-2-one (29) underwent a new versatile addition-elimination (trans-vinylation) reaction with five-membered heterocycles such as furans, pyrroles, imidazole, pyrazole, and 6- (dimethylamino) fulvene to give excellent yields of the corresponding vinylated compounds. This method combined with the intramolecular Diels-Alder reaction was applied to the synthesis of linearly condensed tricyclic heterocycles like psoralen (31) and the novel aza-analogue of psoralen (38). (3) Intramolecular cycloaddition (ex., Diels-Alder reaction) using allenic dienophiles proceeded with extraordinary ease due to their favorable geometry. These reactions were successfully utilized in the development of new polycyclic lactone synthesis, furan ring transfer (FRT) reactions, tandem intramolecular [2+2] -cycloaddition, [3, 3] -sigmatropic rearrangement, and indole synthesis. Application of some of these new methods to the natural products synthesis is also described.
著者
寺尾 秦次
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.45, no.1, pp.2-13, 1987-01-01 (Released:2009-11-13)
参考文献数
64
被引用文献数
2 3

As successive discoveries were made of thromboxane A2, prostacyclin, and the leukotrienes from 1975 to 1979, the physiological and pathological roles of the arachidonate cascade metabolites were clarified. With these discoveries as a turning point, novel concepts for designing new drugs which specifically control and manipulate the metabolites have rapidly grown and developed.Any new approach to treating and preventing cardio- and cerebro- vascular diseases requires urgent and careful evaluation. Recent research into thromboxane synthetase inhibitors (TXSI) and thromboxane receptor antagonists (TXRA) has focussed attention mainly on platelets and blood vessel walls, and the interaction between the two. Some TXSI and TXRA have been studied in a variety of in vitro systems and animal models, and are now in various stages of clinical evaluation.In the present review, TXSI, TXRA, and the structure-activity relationships are described together with the results of our experiments on this subjects.
著者
篠崎 清
出版者
社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.49, no.10, pp.947-948, 1991 (Released:2009-11-16)
参考文献数
10

トリエチレンジアミンはIUPAC命名法では1, 4-diazabicyclo [2.2.2] octaneと命名される.2個の窒素に3個のエチレン基が結合したユニークなジ三級アミンであり窒素原子が露出し立体障害の無い良くまとまった対称構造を持っている。そのためポリウレタン化反応触媒として主に使用され, イソシアナート基 (-NCO) と水酸基 (-OH) の反応において活性が大きく重付加反応と泡化反応の両方のバランスを保つ効果がある。
著者
金子 正勝
出版者
社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.49, no.11, pp.989-1001, 1991
被引用文献数
8

Recent development in the synthetic chemistry of the antitumor antimetabolites of nucleic acid related compounds has been reviewed. In addition to the methodology of the synthesis of antimetabolites from the point of synthetic chemistry, the antitumor activities and the mechanisms of them have also been mentioned.
著者
杉原 多公通 山口 雅彦 西沢 麦夫
出版者
社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.57, no.3, pp.158-169, 1999-03-01 (Released:2009-11-16)
参考文献数
23
被引用文献数
5 7

Cyclic cotrimerization of an alkyne, an alkene, and carbon monoxide mediated by dicobalt octacarbonyl, which is well known as the Pauson-Khand reaction, was promoted by the addition of certain Lewis bases. Primary amines with secondary alkyl groups, such as cyclohexylamine, promoted the stoichiometric Pauson-Khand reaction to give the desired cyclopentenones in good yields. The same reaction can be conveniently carried out in 1, 4-dioxane-aqueous NH4OH biphasic system. Some reactive cobalt complexes might be produced as the coproduct in the reaction mixture and decomposed the substrate and/or the product in some cases. To overcome this disadvantage, alkyl methyl sulfides were introduced as the promoter. The catalytic Pauson-Khand reaction was also promoted by the addition of a tiny amount of DME or water. A novel decomplexation method of alkyne-dicobalt hexacarbonyl complexes by using ethylenediamine and a hydrocarbamoylation reaction were also presented.
著者
増田 克忠
出版者
社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.30, no.3, pp.271-279, 1972-03-01 (Released:2009-11-13)
参考文献数
86
被引用文献数
2 2