Conformer Pair Contributions to Optical Rotations in a Series of Chiral Linear Aliphatic Alcohols

doi:10.1007/s40242-018-8182-2

高等学校化学研究 ›› 2019, Vol. 35 ›› Issue (1): 109-119.doi: 10.1007/s40242-018-8182-2

Conformer Pair Contributions to Optical Rotations in a Series of Chiral Linear Aliphatic Alcohols

ZHAO Dan¹, REN Jie¹, XIONG Yongfei¹, DONG Mengxiang¹, ZHU Huajie¹, Charles U. PITTMAN, Jr.²

1. School of Pharmacy, Hebei University, Baoding 071002, P. R. China;
2. Department of Chemistry, Mississippi State University, Starkville 39762, MS, US

收稿日期:2018-05-31 修回日期:2018-07-11 出版日期:2019-02-01 发布日期:2018-09-29
通讯作者: ZHU Huajie E-mail:hjzhu2017@163.com
基金资助:
Supported by the Scientific Research Foundation of Hebei Educational Committee, China(No.ZD2017004) and the Talent Program of Hebei University, China.

Conformer Pair Contributions to Optical Rotations in a Series of Chiral Linear Aliphatic Alcohols

ZHAO Dan¹, REN Jie¹, XIONG Yongfei¹, DONG Mengxiang¹, ZHU Huajie¹, Charles U. PITTMAN, Jr.²

1. School of Pharmacy, Hebei University, Baoding 071002, P. R. China;
2. Department of Chemistry, Mississippi State University, Starkville 39762, MS, US

Received:2018-05-31 Revised:2018-07-11 Online:2019-02-01 Published:2018-09-29
Contact: ZHU Huajie E-mail:hjzhu2017@163.com
Supported by:
Supported by the Scientific Research Foundation of Hebei Educational Committee, China(No.ZD2017004) and the Talent Program of Hebei University, China.

摘要/Abstract

摘要： The chain length effect of four chiral aliphatic alcohols, (S)-2-butanol, (S)-2-pentanol, (S)-2-hexanol and (S)-2-heptanol, on their specific optical rotations (OR) was studied experimentally and theoretically via quantum theory. Many conformations of each chiral alcohol exist as conformer pairs in solution. The OR sum from these pairs of conformers has much smaller contributions to OR values than that contributed by the most stable conformation. These four alcohols' OR values were also investigated using the matrix model, which employs each substituent's comprehensive mass, radii, electronegativity and symmetry number as the elements in the matrix. These are all particle properties. This matrix determinant is proportional to its OR values within a closely related structural series of chiral compounds. The experimental OR values and the matrix determinants of these four alcohols were compared with the predicted OR values obtained from quantum theory wave functions. The ORs predicted by the matrix method, which is based on particle function statistics, agreed with the results from quantum theory. The agreement between OR predictions by the matrix method and DFT calculations illustrates the wave-particle duality of polarized light that is operating in these predictions.

关键词: Optical rotation, Absolute configuration, Conformer pair, Matrix model, Quantum computation

Abstract: The chain length effect of four chiral aliphatic alcohols, (S)-2-butanol, (S)-2-pentanol, (S)-2-hexanol and (S)-2-heptanol, on their specific optical rotations (OR) was studied experimentally and theoretically via quantum theory. Many conformations of each chiral alcohol exist as conformer pairs in solution. The OR sum from these pairs of conformers has much smaller contributions to OR values than that contributed by the most stable conformation. These four alcohols' OR values were also investigated using the matrix model, which employs each substituent's comprehensive mass, radii, electronegativity and symmetry number as the elements in the matrix. These are all particle properties. This matrix determinant is proportional to its OR values within a closely related structural series of chiral compounds. The experimental OR values and the matrix determinants of these four alcohols were compared with the predicted OR values obtained from quantum theory wave functions. The ORs predicted by the matrix method, which is based on particle function statistics, agreed with the results from quantum theory. The agreement between OR predictions by the matrix method and DFT calculations illustrates the wave-particle duality of polarized light that is operating in these predictions.

Key words: Optical rotation, Absolute configuration, Conformer pair, Matrix model, Quantum computation

ZHAO Dan, REN Jie, XIONG Yongfei, DONG Mengxiang, ZHU Huajie, Charles U. PITTMAN, Jr.. Conformer Pair Contributions to Optical Rotations in a Series of Chiral Linear Aliphatic Alcohols[J]. 高等学校化学研究, 2019, 35(1): 109-119.

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Conformer Pair Contributions to Optical Rotations in a Series of Chiral Linear Aliphatic Alcohols

Conformer Pair Contributions to Optical Rotations in a Series of Chiral Linear Aliphatic Alcohols

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