Enantioselective permeation of various racemates through an optically active poly{1-[dimethyl(10-pinanyl)silyl]-1-propyne} membrane

Macromolecules

Volumn 29, Issue 12, 1996, Pages 4192-4198

  Aoki, Toshiki ^a   Shinohara, Ken Ichi ^a   Kaneko, Takashi ^a   Oikawa, Eizo ^a  

^a NIIGATA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

COPOLYMERS; MECHANICAL PERMEABILITY; OPTICAL RESOLVING POWER; PERVAPORATION; POLYMERIZATION; SOLVENTS; SYNTHESIS (CHEMICAL);

CHIRAL PINANYL GROUP; ENANTIOMER; ENANTIOSELECTIVE PERMEATION; ENANTIOSELECTIVITY; EVAPOMEATION; HOMOPOLYMERIZATION; PERMSELECTIVITY; RACEMATES;

POLYMERIC MEMBRANES;

EID: 0030567644     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma9517254     Document Type: Article

References (20)

1. Morrison, J. D. Asymmetric Synthesis, Analytical Methods; Academic Press: New York, 1983.
2. Newcomb, M.; Helgeson, R. C.; Cram, D. J. J. Am. Chem. Soc. 1974, 96, 7367.
3. Kakuchi, T.; Yokota, T.; Yokota, K. Polym. J. 1990, 22, 199.
4. Maruyama, A.; Adachi, N.; Takatsuki, T.; Torii, M.; Sanui, K.; Ogata, N. Macromolecules 1990, 23, 2748.
5. Aoki, T.; Tomizawa, S.; Oikawa, E. J. Membr. Sci. 1995, 99, 117.
6. Yashima, E.; Noguchi, J.; Okamoto, Y. J. Appl. Polym. Sci. 1994, 54, 1087.
7. Nakagawa, T.; Toyokawa, Y.; Abe, M.; Higuchi, A. Macromol. Symp. 1994, 84, 209.
8. Ishihara, K.; Suzuki, N.; Matsui, K Nippon Kagaku Kaishi 1987, 3, 446.
9. Masuda, T.; Isobe, E.; Higashimura, T. Macromolecules 1985, 18, 841.
10. Aoki, T.; Shinohara, K.; Oikawa, E. Makromol. Chem., Rapid Commun. 1992, 13, 565.
11. Shinohara, K.; Aoki, T.; Oikawa, E. Polymer 1995, 36, 2403.
12. Aoki, T.; Maruyama, A.; Shinohara, K.; Oikawa, E. Polym. J. 1995, 27, 547.
13. Rekker, R. P. The Hydrophobie Fragmental Constant; Elsevier: Amsterdam, 1977.
14. The values of P and % ee for the initial period indicate the values before or near the permeation time when one enantiomer has permeated and the other has not permeated through a membrane.
15. We reported in our previous communication (ref 10) that the permeation under similar conditions showed an (S)-Trp permselectivity, opposite to the result of this paper. In the communication, the % ee was determined by using a polarimeter. After the communication was published, the % ee of the identical sample was determined by using a chiral HPLC instead of a polarimeter and the permselectivity was found to be (R)-Trp permselectivity, identical to the results of this paper. In addition, the (R)-Trp permselectivity was reproducibly observed. Therefore, R selectivity is true. In a later investigation, we found the observation of the opposite selectivity to be due to small amounts of some impurities in the ion-exchange water used in the polarimeter measurement. Since in the polarimeter measurement the water solvent (20 mL) was removed from the permeate and the resulting solid was dissolved in water (1 mL) again, the impurities were concentrated. In order to avoid the contamination, distilled water was used instead of the ion-exchange water in this study.
16. Small peaks other than that of 1,3-BD were for some impurities which 1,3-BD used for the feed contains originally. In an initial period, some impurities were concentrated by the membrane permeation.
17. Since racemic 1,3-BD cannot be separated by a chiral HPLC at present, it is derivatized to the acetate and then analyzed by the HPLC.
18. The difference of the absolute value of the specific rotation between the permeates through a (-)-poly(DPSP) membrane and that through a (+)-poly(DPSP) membrane may be ascribed to the difference of the period of the permeation time. The former permeation was during an initial period and the latter was after the initial period.
19. Budavari, S., Ed. The Merck Index, 11th ed.; Merck and Co: Rahway, NJ, 1989; p 1357. Sodium azide is a cytochrome oxidase inhibitor and was usually used as an antiseptic for the enantioselective permeation experiment. For example: Yoshikawa, M.; Izumi, J.; Kitao, T.; Koya, S.; Sakamoto, S. J. Membr. Sci. 1995, 108, 171.
20. Budavari, S., Ed. The Merck Index, 11th ed.; Merck and Co: Rahway, NJ, 1989; p 1357. Sodium azide is a cytochrome oxidase inhibitor and was usually used as an antiseptic for the enantioselective permeation experiment. For example: Yoshikawa, M.; Izumi, J.; Kitao, T.; Koya, S.; Sakamoto, S. J. Membr. Sci. 1995, 108, 171.