著者

生塩 孝則 遠藤 寛二 山本 恵司

出版者

公益社団法人 日本薬学会

雑誌

YAKUGAKU ZASSHI (ISSN:00316903)

巻号頁・発行日

vol.116, no.11, pp.866-875, 1996-11-25 (Released:2008-05-30)

参考文献数

21

被引用文献数

3 4

---

The physicochemical properties of the enantiomer and racemates of suplatast tosilate (ST) were investigated by means of infrared spectroscopy, solid-state 13C CP/MAS NMR spectroscopy, thermal analysis, and X-ray diffraction analysis, and by measuring the solubility and hygroscopy. The infrared and NMR spectra and X-ray diffraction pattern of the enantiomer were distinctly different from those of the racemate. The melting point of the enantiomer was lower than that of the racemate by 5°C, while the solubility of the enantiomer was 1.3 times higher than that of the racemate. The hygroscopic rate of the enantiomer was greater than that of the racemate. These results suggested that ST was classified into a racemic compound crystal. Furthermore, by comparing the relative peak intensity ratios on X-ray diffraction patterns of crystals with various optical purities prepared by recrystallization, it was found that a mixture of racemic compound crystals and either of racemic mixture crystals or racemic solid solutions was obtained by recrystallization of ST in the content of 0 to 64%ee, while the recrystallization of ST in the content of more than 64%ee led to the formation of racemic mixture crystals or racemic solid solutions.

著者

生塩 孝則

出版者

千葉大学

巻号頁・発行日

1997

---

学位:千大院薬博乙第190号

著者

田村 類 高橋 弘樹 生塩 孝則

出版者

公益社団法人 日本化学会

雑誌

日本化学会誌 (ISSN:03694577)

巻号頁・発行日

vol.2001, no.2, pp.71-82, 2001 (Released:2004-02-20)

参考文献数

31

---

有機ラセミ結晶の新しい自然光学分割現象を見いだし,これを優先富化現象と命名した.ラセミ結晶が優先富化現象を示すための必要条件を明らかにし,その機構を解明することを目的として,優先富化現象を示す化合物の誘導体や類縁体を合成し,これらの化合物の分子 · 結晶構造と優先富化現象の相関関係,これらのラセミ結晶の形態(ラセミ化合物,ラセミ混合物,ラセミ混晶の別)について系統的な研究を行った.その結果,X線結晶構造解析と融点相図の作成により,優先富化現象を示す化合物のラセミ結晶の形態は,きわめて秩序の高いラセミ化合物型の鏡像体間の混晶,あるいは中程度の秩序を持つ鏡像体間の混晶であることが判明した.一方,優先富化現象を示さない化合物のラセミ結晶の形態は,きわめて秩序の低い鏡像体間の混晶であることが示された.また,溶液中での鏡像体の会合構造を保持したまま結晶化したと考えられる結晶構造を得ることができたので,この構造を基にして,優先富化現象と密接に関連する結晶多形転移の機構を提唱する.

著者

田村 類 高橋 弘樹 生塩 孝則

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.56, no.1, pp.22-33, 1998-01-01 (Released:2009-11-16)

参考文献数

16

被引用文献数

1 3

---

We have discovered the first case of accomplishment of an enantiomeric resolution by simple recrystallization of a series of racemic compounds [(±) forms] composed of a regular packing of (+) and (-) molecules in a crystal, although in principle this sort of enantiomeric resolution has been considered to be infeasible for more than a century since the discovery of chiral crystals by Pasteur and preferential crystallization of conglomerates by Gernetz which are a mixture of homochiral (+) and (-) crystals. We have designated this new enantiomeric resolution phenomenon as “Preferential Enrichment”. Here we report a distinct evidence that polymorphism between a racemic compound and a mixed crystal (solid solution), which consists of alternating alignment of the two homochiral dimers in a crystal, is responsible for the “Preferential Enrichment”, and we propose a mechanism of the phenomenon of the reversal of chirality in the deposited crystals, that is the essence of the “Preferential Enrichment”, on the basis of the polymorphic transformation during crystallization.

著者

生塩 孝則 遠藤 寛二 山本 恵司

出版者

公益社団法人日本薬学会

雑誌

藥學雜誌 = Journal of the Pharmaceutical Society of Japan (ISSN:00316903)

巻号頁・発行日

vol.116, no.11, pp.866-875, 1996-11-25

参考文献数

20

被引用文献数

4

---

The physicochemical properties of the enantiomer and racemates of suplatast tosilate (ST) were investigated by means of infrared spectroscopy, solid-state <SUP>13</SUP>C CP/MAS NMR spectroscopy, thermal analysis, and X-ray diffraction analysis, and by measuring the solubility and hygroscopy. The infrared and NMR spectra and X-ray diffraction pattern of the enantiomer were distinctly different from those of the racemate. The melting point of the enantiomer was lower than that of the racemate by 5&deg;C, while the solubility of the enantiomer was 1.3 times higher than that of the racemate. The hygroscopic rate of the enantiomer was greater than that of the racemate. These results suggested that ST was classified into a racemic compound crystal. Furthermore, by comparing the relative peak intensity ratios on X-ray diffraction patterns of crystals with various optical purities prepared by recrystallization, it was found that a mixture of racemic compound crystals and either of racemic mixture crystals or racemic solid solutions was obtained by recrystallization of ST in the content of 0 to 64%ee, while the recrystallization of ST in the content of more than 64%ee led to the formation of racemic mixture crystals or racemic solid solutions.