著者

若林 秀夫

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.48, no.2, pp.164-166, 1990-02-01 (Released:2009-11-13)

被引用文献数

1 2

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乳酸は, 旧約聖書の創世紀の頃からすでに知られており, 化学的に単離したのはSheele (1780) で, 発酵した牛乳からシロップ状の酸を得て, 乳酸と命名した。またBerzelius (1807) は, 筋肉中よりこれによく似た酸 (d-酸) を分離したが, この二つの酸が同一物質であることはWislicenusにより1873年にようやく証明された。即ちSheeleの乳酸はラセミ体で光学活性のない乳酸であり, 筋肉から得られたものは右旋光性の乳酸(d-乳酸) であった。このように乳酸にはL体とD体の光学異性体と, 光学活性のないDL体が存在する。また乳酸と言えば通常α-オキシ・プロピオン酸CH3CH (OH) COOH (分子量C3H6O3=90.08) のことを言う

著者

桐生 知男

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.17, no.9, pp.564-568, 1959-09-01 (Released:2010-10-20)

参考文献数

23

著者

浅原 時泰

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.72, no.6, pp.728-729, 2014-06-01 (Released:2014-07-16)

参考文献数

12

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Nitroso compounds have drawn much attention of synthetic organic and biological chemists because of their usefulness as synthetic intermediate as well as interesting bioactivity. Here, a recent report about the simple and selective preparative method for nitrosoarenes using nitrosonium tetrafluoroborate is described. It provides versatile nitrosoarenes including heteroarenes which are not easily prepared by alternative method.

著者

山中 宏 坂本 尚夫

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.43, no.10, pp.951-961, 1985 (Released:2009-11-13)

参考文献数

118

被引用文献数

7 11

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In the first half of the present paper, the methods with experimental simplicity for the preparation of various alkyl (aryl) pyrimidines are reviewed. In the second half, the reactions of alkylpyrimididines are described in view of synthetic chemistry. Some of these are utilizable for the construction of carbon functional groups on pyrimidine rings.

著者

青山 幸造

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.11, no.10, pp.391-393, 1953-10-30 (Released:2010-10-20)

参考文献数

1

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ルイサイトの製造に際し副生する第二アルシンはこれに理論量の1.5倍の三塩化砒素を混合し更に2%の栄種油を触媒として加え150℃ に2時間加熱することにより第一アルシンと第二アルシンとの重量比約70: 30の組成のものにすることが可能である。なお此の場合の平衡状態に関し若干の考察を加えた。

著者

青山 幸造

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.11, no.9, pp.347-352, 1953-09-30 (Released:2010-10-20)

参考文献数

16

被引用文献数

2

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種々実験の結果最適合成条件は次記の如くであることを知つた。即ち濃度25-30%塩酸600c. c. に塩化第一銅100gを溶解した母液中に三塩化砒素の100gを加え30-60℃に於いて攪拌しつつアセチレンを30-40cc/minにて20l導入した後粗油を分離これを蒸溜することにより85%の牧率でルイサイトを得られる。中規模実験の結果も良好な成果を挙げることが出来た。

著者

桑嶋 功

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.37, no.2, pp.107-118, 1979-02-01 (Released:2009-11-13)

参考文献数

56

被引用文献数

2 2

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Several organosilicon compounds have been prepared through reductive silylation reaction with NaMe3SiCl and their synthetic utilities for specific carbon bond formations have been described.

著者

吉田 泰志

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.76, no.1, pp.55-56, 2018-01-01 (Released:2018-01-16)

参考文献数

15

被引用文献数

1

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Regio- and stereoselective synthesis of organoboron compounds has great importance due to their wide applicability and high stereospecificity in many transformations such as Suzuki-Miyaura cross coupling reaction. Generally, hydroboration of unactivated terminal alkenes proceeds in anti-Markovnikov selective manner to produce linear products. In this short review, recent examples of catalytic Markovnikov hydroboration of unactivated terminal alkenes, and its application to asymmetric synthesis are described.

著者

熊野谿 従 桑田 勉

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.11, no.10, pp.388-390, 1953-10-30 (Released:2010-10-20)

参考文献数

7

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サリチルアルデヒド・無水酢酸を酢酸ナトリウムを触媒として反応せしめ理論牧率50%でクマリンを合成し, 従来の文献値を24%凌駕した。この反応で特に酢酸の存在で生成し易いサリチルアルデヒドトリアセテートは反応中に殆んど分解して無水酢酸とサリチルアルデヒドモノアセテートとなり酢酸ナトリウムの存在で始めてアルドール縮合を行いクマリンをつくることと単体では加熱してもクマリンを生球しないこととを実験によつてたしかめた。

著者

大前 巌

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.2, pp.133-145, 1978-02-01 (Released:2009-11-13)

参考文献数

99

被引用文献数

2 2

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1, 4-Cyclohexadiene (1, 4-CHD) is easily prepared by the Birch reduction using an alkali metal and a proton source in liquid ammonia or by the electrolytic reduction, and the 1, 4-CHD can be isomerized to 1, 3-CHD and disproportionated to benzene and cyclohexene or cyclohexane. While the addition reaction of one double bond in the 1, 4-CHD occurs easily, the reactivity of the other double bond is lowered. As the disproportionation and the hydrogenation are carried out using the same catalyst, it seems reasonable that the reaction of the 1, 4-CHD with the catalyst forms once a π-complex, the 1, 4-CHD moiety of the π-complex is eliminated as benzene by heating, the remaining catalyst moiety having two hydrogen atoms of the complex reacts with the other 1, 4-CHD molecule to form the hydrogenated π-complex, which gives cyclohexene. The 1, 4-CHD forms the 1, 4-, 1, 3-CHD of phenyl-π- complexes depending upon various kinds of metals of the catalyst, and the mass spectra of the 1, 3-π- complex indicates the presence a metastable ion during the cource from the molecular ion to the dehydrogenated phenyl-π-complex ion. The polymerizability of 1, 4-CHD monomer is low and poly-1, 3-CHD-, polymer of a low molecular weight is formed after the isomerization to 1, 3-CHD in the polymerization. Its oxidation affords diepoxide and tetraol which can be used as polymers and modifiers, and its reaction with metal cyanide and phosgene affords tetracyanoquinodimethane which can be also used as conductive polymers and super conduction materials.

著者

浅尾 豊信 伊東 俊司

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.54, no.1, pp.2-14, 1996-01-01 (Released:2010-01-28)

参考文献数

51

被引用文献数

4 4

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Studies in our laboratory on the syntheses of hydroxyazulenes, azulene thiols, polyaminoazulenes, and azulene analogue of carixarene, and on the synthesis, stabilities, and dynamic stereochemistries of extremely stable carbocations containing azulene were reviewed. 2- And 6- hydroxyazulenes were synthesized as stable crystals, which were found to exist as their keto- and enol-forms depend on the solvent used. 1-Hydroxyazulene and 3-hydroxyguaiazulene were synthesized starting from the corresponding benzoyloxyazulenes as extremely unstable compounds, and the latter was found to isomerize to a mixture of its keto form and oxidative dimers. 1-, 2-, and 6-azulene thiols, and 1, 2-diamino- and 1, 2, 3-triaminoazulene derivatives were synthesized as stable compounds. A series of azulene analogues of triphenylmethyl cation; tri (1-azulenyl) methyl, di (1-azulenyl) phenylmethyl, and (1-azulenyl) diphenylmethyl hexafluorophosphates and their various derivatives were synthesized by hydride abstraction of the corresponding methane derivatives with DDQ. Their pKR+values showed that the stabilities of these cations dramatically increase with the number of azulene rings. Tris (3, 6-di-t-butyl-1-azulenyl) methyl cation showed the highest pKR+ value (14.3) ever observed. The dynamic stereochemistries of these cations were also studied based on the temperature-dependent NMR spectra, which were analyzed by a flip mechanism. First example of one-ring flip mechanism was found for these molecular propellers. Extremely stable di- and trications were also synthesized.

著者

荒井 孝義

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.76, no.1, pp.3-10, 2018-01-01 (Released:2018-01-16)

参考文献数

89

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A chiral N,N,N-terdentate bis(imidazolidine)pyridine (PyBidine) has showed remarkable ligand acceleration effects in various metal catalyzed asymmetric reactions. For an example, PyBidine-Cu(OTf)2 catalyzed a highly endo-selective [3+2] cycloaddition of nitroalkenes with imino esters. X-ray crystallographic analysis of the PyBidine-Cu(OTf)2 complex and DFT calculations suggest that an intermediary generated Cu-enolate of the imino ester reacts with nitroalkenes, which are activated by NH-proton of imidazolidine ligand. Based on the intelligent role of imidazolidine, a new chiral imidazolidine-containing NCN palladium pincer complex (tBu-PhBidine-PdX) was prepared by a ligand introduction route. The neutral tBu-PhBidine-PdCl complex demonstrated significant catalytic activity for the reaction of nitroalkenes with malononitrile to give the products in good yields with high enantioselectivities. On the contrary, the cationic chiral imidazolidine-containing tBu-PhBidine-PdOTf catalyst promoted the nucleophilic addition of unprotected indoles to N-Boc imines. Using sulfinyl amines as the N-Boc imine precursors, the combined use of catalyst with K2CO3 activated the N-H-free indoles to give chiral 3-indolyl methanamines with up to 98% ee. Compared with conventional acid-catalyzed Friedel-Crafts reactions, this reaction proceeding under mildly basic conditions shows advantages for the use of acid-sensitive substrates. Furthermore, chiral bis(imidazolidine)-containing PhBidine-Rhodium complexes (PhBidine-RhX2 and tBu-PhBidine-RhX2) were prepared by a C-H insertion method. The tBu-PhBidine-Rh(OAc)2 smoothly catalyzed an asymmetric Mannich reaction of malononitrile with N-Boc imines to give products, which are useful for the synthesis of chiral α-amino acids.

著者

宇根山 健治

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.55, no.12, pp.1081-1091, 1997-12-01 (Released:2009-11-16)

参考文献数

74

被引用文献数

4 6

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Generation and synthetic utilization of highly reactive fluorinated intermediates, which include chemistries of trifluoroacetimidoyl halides, electrochemical activation of fluorinated organic compounds, and chalcogen molecule mediated fluorinations, are discussed.Synthesis of optically active trifluoroalanine via trifluoroacetimidoyl palladium intermediates, generation of trifluoroacetimidoyl radicals, electrochemical synthesis of 2-CF3-benzimidazoles, chemistry of benzeneselenenyl fluoride, and SET process between benzeneselenolate anion and fluorinated alkylhalides are highlight of this overview.

著者

深瀬 泱

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.55, no.10, pp.920-925, 1997 (Released:2009-11-16)

参考文献数

6

被引用文献数

9 11

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Voglibose (1, N- [2-hydroxy-1- (hydroxymethyl) ethyl] valiolamine, basen®), having more potent disaccharidase inhibitory activity against maltase and sucrase than do naturally occurring pseudo-oligosaccharide α-glucosidase inhibitors, has been developed for the treatment of diabetes mellitus as the blood glucose ameliorating agent. Valiolamine (2), an important key compound for the preparation of N-substituted valiolamine derivatives such as 1, was synthesized by stereoselective hydration of the carbon-carbon double bond of valienamine (3) obtained by microbiological degradation of validamycins. Efficient and practical total synthesis of 2 starting from D-glucose has also been achieved.In animals and healthy volunteers, voglibose (1) significantly reduced postprandial blood glucose concentration. Clinical trials in patients with diabetes mellitus also demonstrated that 1 improves post-pratial glucose levels. In Japan, 1 was approved in July, 1994.

著者

利部 伸三

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.58, no.6, pp.606-610, 2000-06-01 (Released:2009-11-13)

参考文献数

3

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イミダクロプリドは1991年に上市されて以来現在76国に登録され, 1998年には6億USドルと世界最大の売り上げを記録した殺虫剤である。一方カルプロパミドは1998年に上市された稲いもち病防除剤である。筆者は企業の研究所において7年間農薬創製研究に携わる機会を得て, 表題の2薬剤を最初に合成する幸運に恵まれた。本稿は大学で合成有機化学を学んだ一人が企業で未経験の分野に足を踏み入れ, 商品化合物の発見に至った道のりを回想したものである。両薬剤に関する詳細な構造活性相関, 作用機構や応用に関しては総説を参照していただきたい。なお筆者がすべての賞に含まれているわけではないが, イミダクロプリドの発明・研究に対しては, 日本農薬学会賞 (技術), 同 (研究), 全国発明特別賞, 大河内賞, アメリカ化学会賞等, カルプロパミドに対しては日本農薬学会賞 (技術) 等が与えられている。

著者

斉藤 軍治 岡田 尚子

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.6, pp.502-514, 1987-06-01 (Released:2010-01-22)

参考文献数

36

被引用文献数

3 4

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An overview of a series of tetrachalcogenafulvalene derivatives and their charge transfer complexes is presented in connection with the molecular designing of molecular conductors of one component (molecular fastener and chalcogen-chalcogen chain compound), organic metals, organic superconductors, complex isomerization, and other functional molecular assembly.

著者

岩村 秀

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.52, no.4, pp.295-307, 1994-04-01 (Released:2009-11-16)

参考文献数

35

被引用文献数

1 2

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There are two approaches toward the establishment of macroscopic spins for organic molecules. One is the exploration of persistent free radicals (S=1/2) that will have ferromagnetic interradical exchange coupling in crystalline states. While this approach has led to the discovery of well characterized organic ferromagnets, their Curie temperatures (Tc) are limited to sub-liquid-helium temperatures. Alternatively, design and synthesis of super-high-spin (S>>1/ 2) organic molecules have been studied. In principle, parallel alignment of two spins can become favored in non-Kekulé systems. One of the highlights of the oligomers and polymers obtained by repeating such units is the synthesis and characterization of a strongly paramagnetic nonacarbene (S=9). The two-dimensional network alignment of spins has been demonstrated to be most promising as high Tc molecular ferromagnets. Some non-Kekulé molecules were found by EPR spectroscopy and magnetic susceptibility/magnetization measurements to violate Hund's rule, thereby being disqualified as the units for super-high-spin polymers.

著者

Munetaka KUNISHIMA Shohei TANI

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

Journal of Synthetic Organic Chemistry, Japan (ISSN:00379980)

巻号頁・発行日

vol.57, no.2, pp.127-135, 1999-02-01 (Released:2009-11-16)

参考文献数

31

被引用文献数

7 7

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Reduction of aryl and vinyl radicals to the corresponding organosamarium species by SmI2 can be attained by using benzene-HMPA as a solvent system. Thus, SmI2-mediated Barbier- and Grignardtype coupling reactions between ketones and aryl, vinyl, or alkynyl iodides proceed via organosamarium species in benzene-HMPA. Reductive dehalogenation of 1, 1-dihaloalkenes by SmI2 in benzene-HMPA generates alkylidenecarbenes, which undergo either 1, 5-C-H insertion giving cyclopentenes or 1, 2-shift giving alkynes. On the other hand, SmI2 was found to be useful to effect 2, 3-rearrangement under mild conditions. Metalated ethers undergoing Wittig rearrangement are regioselectively generated by either an intramolecular 1, 5-hydrogen transfer of a vinyl radical, generated by a single electron transfer from SmI2 to γ-haloallyl ethers, or a net two-electron reduction of diallyl acetals with the liberation of an allyloxy samarium by SmI2 in acetonitrile. 2, 3-Rearrangement of allylic sulfonium ylides can be effected by the reaction of allylic sulfides with samarium carbenoid, generated from CH2I2 and SmI2 in THF.

著者

亀谷 哲治 気賀沢 和雄

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.29, no.3, pp.227-236, 1971-03-01 (Released:2009-11-16)

参考文献数

73

被引用文献数

2 1

著者

酒井 浄

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.29, no.3, pp.205-226, 1971-03-01 (Released:2010-01-28)

参考文献数

51

被引用文献数

2 1