Cis-trãns Isomeric Carotenoids Vitamins A and Arylpolyenes

by Laczlo Zechmeister

Overview

The core of this little book is a survey of the experimental work carried out by our research group in the course of two decades. Although the writer has made an effort to present and evaluate related contributions of many authors, the text should not be considered as a monograph of encyclopedic character. Our experiments began with a study of cis-Irans-isomeric C - 40 carotenoids and were subsequently extended to other types of polyenes in order to determine how far the observations were applicable to broader fields. Similar considerations have led to the inclusion of the Chapters on Vitamins A and on Cumulenes although we have not contributed to the stereochemistry of these classes of compounds. The first eleven Chapters have been published in Volume XVIII of the Series, "Progress in the Chemistry of Organic Natural Products" and now appear in a revised, up-to-date form. Sincere thanks are due to the following former members of our research group who have participated in the experimental elucidition of the field: W. V. Bush, A. Chatterjee, L. Cholnoky, J. Dale, R. B. Escue, P. Fischer Jorgensen, Ch. Gansser, F. T. Haxo, G. Karmakar, B. K. Koe, J. Leemann, R. M. Lemmon, the late A. L. LeRosen, W. Lijinsky, K. Lunde, E. F. Magoon, W. H. McNeely, F. J. Petracek, J. H. Pinckard, A. Polgar, A. Sandoval, W. A. Schroeder, J. W. Sease, Y. W. Tang, K. Tsukida, the late P. Tuzson, L. Wallcave, and B. Wille. Dr.

Product Details

ISBN-13:	9783709155509
Publisher:	Springer Vienna
Publication date:	03/11/2012
Edition description:	Softcover reprint of the original 1st ed. 1962
Pages:	252
Product dimensions:	6.10(w) x 9.25(h) x 0.02(d)

Table of Contents

First Part: Isoprenic Polyenes.- I. Carotenoids: Introduction.- Nomenclature.- Some Historical Remarks on the Stereoisomerism of Polyenes.- II. Number and Types of cis Carotenoids. Steric Hindrance.- III. Some Properties of cis Carotenoids.- 1. Relative Stabilities.- Sterically Unhindered cis Forms.- Sterically Hindered cis Forms.- Polycis Forms.- 2. Melting Points.- 3. Rotatory Power.- 4. Relative Adsorption Affinities.- IV. Cis-trans Isomerism and UV Spectra.- 1. Some Remarks on the Spectra of all-trans Carotenoids.- 2. Spectral Effect of trans— cis Isomerization in the Visible Region.- 3. Spectral Effect of trans— cis Isomerization in the Near Ultraviolet Region: the cis-Peak.- 4. A Simple theoretical Interpretation of Spectral Phenomena, Especially of the cis-Peak Effect.- 5. Spectra at Extremely Low Temperatures.- V. Preparation of cis Carotenoids by Direct Rearrangement of the All-trans Form.- 1. Thermal Methods of cis-trans Isomerization.- a. Spontaneous Rearrangements in Solution at Room Temperature.- b. cis-trans Isomerization in Refluxed Solutions.- c. cis-trans Isomerization by Melting Crystals.- 2. Phohemical cis-trans Isomerization in the Absence of Catalysts.- 3. cis-trans Isomerization by Iodine Catalysis, in Light.- 4. cis-trans Isomerization by Acid Catalysis.- 5. cis-trans Isomerization by Contact with Active Surfaces.- 6. cis-trans Isomerization via Boron Trifluoride Complexes.- 7. Bio-stereoisomerization.- VI. Preparation of cis Carotenoids by Total Synthesis.- VII. Naturally Occurring cis and Polyds Carotenoids.- 1. Mono- and Dices Carotenoids.- 2. Polycis Carotenoids.- Prolycopene.- Further Polycis Lycopenes.- Proneurosporene (Protetrahydrolycopene, Neoneurosporene P).- Pro-β-carotene.- VIII. Some General Remarks on Configurational Assignments.- 1. Stereoisomeric Types.- 2. Number and Location of cis Double Bonds.- 3. Configuration and Infrared Spectrum.- IX. Configurational Assignments in Certain Stereoisomeric Sets.- 1. Stereoisomeric Sets with Two Hydroaromatic Terminal Groups.-—-Carotene Set.- Cryptoxanthin—Cryptoxanthin) Set.- Zeaxanthin Set.- Isozeaxanthin Set.- Echinenone Set.- Canthaxanthin Set.-—Carotene Monoepoxide Set.-—Carotene Diepoxide Set.- Luteochrome Set.- 3,4-Dehydro-ß-carotene and 3,4,3?,4?Bisdehydro-β-carotene Sets.- 16,I6?-Homo-β-carotene Set.- 13,13'-Bis-desmethyl-β-carotene Set.- retro-Dehydrocarotene Set.-—-Carotene Set.-—-Cryptoxanthin (Physoxanthin) Set.- Lutein Set.- 3,4-Dehydro-ß-carotene Set.- Trollixanthin Set.- Taraxanthin Set.- Capsanthin Set.- Capsorubin Set.- 2. Stereoisomeric Sets with One Hydroaromatic and One Aliphatic Terminal Group.-—-Carotene Set.- Gazaniaxanthin Set.-—-Zeacarotene Set.- Celaxanthin Set.- Torularhodin Set.- 3. Stereoisomeric Sets with Two Aliphatic Terminal Groups.- Lycopene Set.- Neurosporene Set.-—-Carotene Set.- Phytofluene Set.- Phytoene Set.- Rhodoviolascin (Spirilloxanthin) Set.- Fucoxanthin Set.- 4. Stereoisomeric Sets with Two Aromatic Terminal Groups.- 1,18-Diphenyl-3,7,12,16-tetramethyl-octadecanonaene Set.- Renieratene and Isorenieratene Sets.- 1,3,7,12,16,18-Hexaphenyl-octadecanonaene Set.- “Naphthyl-carotene” Set.- X. Lower-molecular Weight Carotenoid-carboxylic Acids: Bixin and Crocetin.- Bixin Set.- Crocetin Set.- XI. Cis-trans Isomerism and Provitamin A Effect of Carotenoids.- XII. Vitamins A and Retinenes.- 1. Structural Relationships.- 2. Number and Character of cis Vitamins A and cis Retinenes.- 3. Cis-trans Isomerism and Spectra.- Ultraviolet Spectra.- UV Spectra at Extremely Low Temperatures.- Infrared Spectra.- 4. Preparation of cis Vitamins A and cis Retinenes by Direct Rearrangement.- a. Thermal Methods of Stereoisomerization.- b. Photo-stereoisomerization in the Absence of Catalysis.- c. Stereoisomerization by Iodine Catalysis.- d. Stereoisomerization by Acid Catalysis.- e. Bio-stereoisomerization.- 5. Preparation of cis Isomers by Total Synthesis.- 6. Naturally Occurring cis Vitamins A and Retinenes.- 7. Chromatographic Separation of Stereoisomers.- 8. Some Methods used in Configurational Assignments.- Spectra.- Esterification Rates.- Dehydration.- Maleic Anhydride Adducts.- Opsin Test.- 9. Systemic Bioeffects of cis-trans Isomeric Vitamins A and Retinenes.- Biochemical Relationship to Carotenes.- Bioeffects and Stereoisomerism.- 10. Some Stereochemical Aspects of Visual Processes.- Retinene Isomerase.- Second Part: Unbranched Arylpolyenes. Introductory Remarks.- XIII. I-Monoaryl-polyenes.- I-Phenylbutadiene Set.- I-Phenulundecapentaenal-(11) Set.- XIV.—,?-Diphenylpolyenes and Related Compounds.- 1. General Remarks.- 2. Stilbene Set.- 3. Diphenylbutadiene Set.- 4. Diphenylhexatriene Set.- 5. Diphenyloctatetraene Set.- 6. Sets Containing Bulky End Groups and a Short Conjugated System.- 2,2?-Diamino-bis-diphenylene-ethylene Set.- 1,2-Bis-[m-nitrophenyl]-1,2-diphenyl-ethylene and 1,2-Bis-[p-nitrophenyl]-1,2-diphenyl-ethylene Sets.- 1-Biphenylene-4-phenylbutadiene, 1-Biphenylene-6-hexatriene, 1,6-Di-biphenylene-hexatriene, and 1,1,6,6-Tetraphenyl-hexatriene Sets.- XV. Cumulenes with. Aromatic Terminal Groups.- Bis-[2-nitrodiphenylene]-butatriene Set.- 1,4-Bis-[m-nitrophenyl]-1,4-diphenyl-butatriene Set.- XVI. Polyene Azines.- Cinnamalazine Set.- Phenylpentadienalazine Set.- XVII. Bibliography.- Index of Authors.- Index of Subjects.