116-31-4Relevant articles and documents
The OSM (Oxidation State Modification) Concept: Application to a New and Rapid Synthesis of Retinoids
Duhamel, Lucette,Duhamel, Pierre,Ancel, Jean-Erick
, p. 1209 - 1210 (1994)
The OSM (oxidation state modification) concept for the elaboration of new synthetic pathways is demonstrated for the synthesis of β-ionylidene acetaldehyde 11 and retinal 13.According to this new scheme, electrophilic addition to ω-heterosubstituted enol ethers 5 of the cationic species 9, generated from β-ionol led to aldehydic intermediates 10 which undergo easy elimination to β-ionylidene acetaldehyde 11.Similarly, retinal 13 was obtained from vinyl-β-ionol 14 and dienol ethers 12, via aldehydes 16.
Mechanism for the Two-bond Isomerization in the Photoirradiation of 7,9-Di-cis-retinal
Liu, Robert S. H.,Zhu, Yun
, p. 1765 - 1766 (1993)
The two-bond isomerization process of 7,9-di-cis-retinal to all-trans-retinal has been shown to proceed by way of an adiabatic, stepwise process.
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Karrer,Rueegger
, p. 284 (1940)
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Retinal isomer composition in some bacteriorhodopsin mutants under light and dark adaptation conditions
Song,Yang,El-Sayed,Lanyi
, p. 10052 - 10055 (1995)
The isomeric composition of retinal was measured in a number of bacteriorhodopsin (bR) mutants (D85N), D212N, R82A, Y185F, and D115N) under various conditions, using a rapid retinal extraction technique followed by HPLC analysis. Besides the 13-cis and the all-trans retinal isomers observed in wild type (wt) bR under physiological conditions, the 11-cis and 9-cis retinal isomers were observed in variable but minor amounts in the bR mutants. In addition, the values of the equilibrium constant at two temperatures and the enthalpy change for the all-trans to 13-cis isomerization process in the dark-adapted state of D212N, D85N, deionized blue bR, and wt bR were determined. We find that perturbation of the retinal cavity (pocket) by residue replacement changes the relative thermal stability of the different retinal isomers, allowing for thermal-and/or photoisomerization of the retinal chromophore along C9-C10 and C11-C12 bonds to moderately compete with the isomerization around the C13-C14 bond. The bR mutants expressed in Halobacterium salinarium studied in the present work showed normal 13-cis to all-trans light adaptation, in contrast with abnormal all-trans to 13-cis light adaptation observed for D212E, D212A, and D212N expressed in Escherichia coli, suggesting an influence of the purple membrane lattice and/or the lipids on the stability of the different retinal isomers within the protein.
Exploratory study of β-carotene autoxidation
Mordi,Walton,Burton,Hughes,Ingold,Lindsay
, p. 4203 - 4206 (1991)
The main products in the early stages of β-carotene autoxidation were epoxides, β-ionone, β-apo-13-carotenone, retinal, and related carbonyl compounds; in the final mixture short chain carbonyl compounds predominated.
Prenylation reaction performed with catalytically generated potassium prenal dienolate
Cahard, Dominique,Duhamel, Lucette,Lecomte, Sandrine,Poirier, Jean-Marie
, p. 1399 - 1401 (1998)
A new prenylation method based on the reaction of catalytically generated potassium dienolate of prenal with α,β-unsaturated aldehydes is described. The reaction is highly regioselective, via a γ-1,2-addition, and provides an efficient route to retinal.
Kondukova et al.
, (1973)
Silica Gel Mediated Photoisomerization of Retinal Isomers and Comparisons with Other Forms of Environmental Pertubation
Zawadzki, Mary E.,Ellis, Arthur B.
, p. 3156 - 3161 (1983)
The electronic spectra and photoreactivity of slurries of retinal isomers, prepared by adsorbing the isomers onto wet silica gel and suspending the support in cyclohexane, have been investigated.Adsorption of 9-cis-, 11-cis-, 13-cis-, and all-trans-retinal is accompanied by an ca. 3000-cm-1 red shift of their lowest energy absorption band maxima relative to their band positions in homogeneous cyclohexane solution.Irradiation of the slurries at 514.5 nm, a wavelength inefficiently absorbed in the absence of silica gel, leads to reasonably efficient photoisomerization of each of these isomers.Prolonged photolysis yields a mixture of the four isomers that is photostationary with respect to relative concentrations and richest in 11-cis-retinal, which constitutes ca. 35percent of this mixture.Although small quantities of other isomers are present, the photostationary composition of the heterogeneous photolysate can be predicted with reasonable accuracy from the relative absorptivities and primary photoprocesses of the four principal isomers comprising the photolysate.Comparisons with primary photoprocesses reported for retinal isomers in polar and nonpolar solvents reveal that adsorption onto silica gel can result in novel patterns of photoisomerization.Complementary comparisons are made with the electronic spectra and photoreactivity of adducts formed in hydrocarbon solution from retinal isomers and a lanthanide β-diketonate complex.The excited-state properties of these various retinal-based systems highlight the impotance of environment in controlling photoreactivity.Steric and electronic factors that may contribute to the observed features of silica gel mediated photoisomerization are discussed in this context.
Palladium-catalysed vinylation of tertiary allylic alcohols: A new protocol for the synthesis of isoprenoid aldehydes.
Bienayme,Yezeguelian
, p. 3389 - 3396 (1994)
Heck vinylation of tertiary allylic alcohols with iodo-acetal Ic, followed by an acid catalysed acetal hydrolysis-dehydration reaction, furnished isoprenoid aldehydes regioselectively in high yields.
Studies on the Catalyzed Interconversions of Vitamin A Derivatives
Rando, Robert R.,Chang, Andrew
, p. 2879 - 2882 (1983)
The kinetics of the I2-catalyzed isomerization of the retinal isomers were studied.The all-trans isomer formed 13-cis-retinal rapidly with a rate constant 1.9E-4 s-1.The reverse reaction occurred with a rate constant of 4.5E-4 s-1.The 11-cis isomer was first converted to all-trans-retinal with a rate constant of 3.1E-4 s-1, although the 13-cis isomer was also rapidly formed.The 9-cis isomer was isomerized to the 9-cis, 13-cis isomer before the other isomers were generated and the 13-cis isomer was converted to its all-trans congener prior to the formation of the other isomers.Similar results appear to occur when other methods of catalysis are used.This isomerization about the C13-C14 double bond appears to be kinetically favored event, eliminating the possibility that 11-cis might be a kinetic product formed from the all-trans isomer.At equilibrium, only 0.1percent of 11-cis-retinal is found.Equilibration of all-trans-retinol palmitate also generated very little of the 11-cis-isomer (/= 0.2percent) 11-cis-retinol palmitate at equilibrium.The implications of these results for an 11-cis-retinal regeneration mechanism in the eye are discussed.
Configurational Changes of Retinal in the Triplet State: Picosecond Time-Resolved Absorption Spectroscopy on the 7-Cis, 11-Cis, and 13-Cis Isomers and High-Performance Liquid Chromatography Analysis of Photoisomerization
Mukai, Yumiko,Koyama, Yasushi,Hirata, Yoshinori,Mataga, Noboru
, p. 4649 - 4653 (1988)
The triplet state of retinal was produced from the 7-cis, 11-cis, and 13-cis isomers by direct excitation with 355-nm ca. 10-ps pulses in deoxygenated n-hexane solution at room temperature.A set of transient absorption spectra was recorded for each isomer, in the time domain within 5 ns after excitation.The results indicated the following: (1) The 7-cis and 11-cis isomers initially produce their own short-lived, primary "7-cis" and "11-cis" triplet species which relax into the common, stationary "all-trans" triplet species. (2) The 13-cis isomer produces two different stationary triplet species, i.e., one its own "13-cis" and the other the above "all-trans" triplet species. (3) The above cis-isomers produce also "all-trans" triplet species immediately after excitation.The presence of two different long-lived, stationary triplet species, which were revealed by a previous study by resonance Raman spectroscopy, is confirmed, and short-lived, primary triplet species produced from the 7-cis and 11-cis isomers have been identified, in addition to the one from the 9-cis isomer, which was identified in a previous transient absorption study.The products of isomerization by benzil-sensitized triplet excitation of the all-trans, 7-cis, 9-cis, 11-cis, and 13-cis isomers were analyzed by means of high-performance liquid chromatography.The major product of isomerization from the cis isomers was the all-trans isomer.On the basis of the above results, the mechanisms of isomerization via the triplet state are discussed.
Broad-spectrum antiviral activity including human immunodeficiency and hepatitis C viruses mediated by a novel retinoid thiosemicarbazone derivative
Kesel, Andreas J.
, p. 1656 - 1664 (2011)
Aromatic aldehyde-derived thiosemicarbazones 4-6, the S-substituted modified thiosemicarbazones 7/8, and a vitamin A-derived (retinoid) thiosemicarbazone derivative 12 were investigated as inhibitors of human hepatitis C virus (HCV) subgenomic RNA replicon Huh7 ET (luc-ubi-neo/ET) replication. Compounds 4-6 and 12 were found to be potent suppressors of HCV RNA replicon replication. The trifluoromethoxy-substituted thiosemicarbazone 6 and the retinoid thiosemicarbazone derivative 12 were even superior in selectivity to the included reference agent recombinant human alpha-interferon-2b, showing potencies in the nanomolar range of concentration. In addition, compounds 5, 6, 8 and 12 were tested as inhibitors of cytopathic effect (CPE) induced by human varicella-zoster virus (VZV) and/or human cytomegalovirus (HCMV). Compounds 4-6, 8 and 12 were additionally examined as inhibitors of CPE induced by cowpox virus and vaccinia virus. Thiosemicarbazone 4 was inhibitory on cowpox and vaccinia virus replication comparable in potency and selectivity to the reference agent cidofovir. Retinoid thiosemicarbazone derivative 12 was active as micromolar inhibitor of VZV, HCMV, and, in addition, human immunodeficiency virus type 1 (HIV-1) replication. These results indicate that thiosemicarbazone derivatives are appropriate lead structures to be evaluated in targeted antiviral therapies for hepatitis C (STAT-C), and that the vitamin A-related thiosemicarbazone derivative 12 emerges as a broad-spectrum antiviral agent, co-suppressing the multiplication of important RNA and DNA viruses.
Monolayer films of retinal-1 and the effects of light on them.
Maeda,Isemura
, p. 765 - 766 (1967)
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Catalytic activities of tumor-specific human cytochrome P450 CYP2W1 toward endogenous substrates
Zhao, Yan,Wan, Debin,Yang, Jun,Hammock, Bruce D.,De Montellano, Paul R. Ortiz
, p. 771 - 780 (2016)
CYP2W1 is a recently discovered human cytochrome P450 enzyme with a distinctive tumor-specific expression pattern. We show here that CYP2W1 exhibits tight binding affinities for retinoids, which have lownanomolar binding constants, andmuch poorer binding constants in the micromolar range for four other ligands. CYP2W1 converts alltrans retinoic acid (atRA) to 4-hydroxy atRA and all-Trans retinol to 4-OH all-Trans retinol, and it also oxidizes retinal. The enzyme much less efficiently oxidizes 17b-estradiol to 2-hydroxy-(17b)-estradiol and farnesol to a monohydroxylated product; arachidonic acid is, at best, a negligible substrate. These findings indicate that CYP2W1 probably plays an important role in localized retinoid metabolism that may be intimately linked to its involvement in tumor development.
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Wald et al.
, p. 438,446 (1955)
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Retinal-based polyene fluorescent probe for selectively detection of Cu2+ in physiological saline and serum
Li, Yang,Lan, Haichuang,Yan, Xia,Shi, Xiaotao,Liu, Xiao,Xiao, Shuzhang
, (2020)
Retinal is a flexible natural chromophore and widely present in organisms. The slender conjugated polyene structure retinal is conducive to entering protein structure. In this work, a novel turn-on fluorescent probe for Cu2+ based on retinal and phenylenediamine was designed and synthesized. The probe achieved recognition of copper ions in human serum complex protein environment. Furthermore, the high sensitivity, selectivity for Cu2+ and the sensing mechanism was also investigated.
Mimicking light-sensing chromophore in visual pigments and determination isomerization site
Li, Yang,Lan, Haichuang,Yan, Xia,Shi, Xiaotao,Liu, Xiao,Xiao, Shuzhang
, (2020/01/02)
Three retinal derivatives are designed and synthesized under the inspiration of natural visual pigments. The retinal derivative V3 (retinal-phenylenediamine) is able to respond sensitively to visual light in the absence of a protein environment through isomerization and deprotonation. The response process is applied to verification of information security.
SPECIFIC DEHYDROGENATION PROCESS (I)
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Page/Page column 11, (2020/10/28)
The present invention relates to a new dehydrogenation process of specific compounds.
