- Ph-dependent photoinduced interconversion of furocoumaric and furocoumarinic acids
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Photo-controlled or photo-regulated molecules, especially biologically active and operating in physiological conditions, are in steady demand. Herein, furocoumaric and furocoumarinic acids being (Z/E)-isomers relative to each other were obtained in two stages starting from psoralen: the alkaline solvolysis of psoralen led to furocoumaric acid, which was further Z → E photoisomerized (365 nm) to furocoumarinic acid. The kinetics of Z → E photoisomerization was monitored by HPLC and UV-vis spectrophotometry. Photophysical characteristics in the aqueous phase for both acids, as well as the reversibility of (Z/E) photoisomerization process, were also assessed. Furocoumarinic acid was found to be visibly fluorescent at pH 2.0–12.0, with the maxima of fluorescence emission spectra being pH-dependent. The reverse E → Z photoisomerization predicted by quantum chemistry calculations as energetically favorable for the monoanionic form of furocoumarinic acid was proved in the experiment while being complicated by pyrone ring closure back to psoralen in acidic and neutral conditions. The preparative synthesis of furocoumarinic acid outlined in this work is particularly valuable in view of a wide range of pharmacological effects previously predicted for this compound.
- Boldyrev, Ivan A.,Malakhov, Mikhail V.,Maslov, Mikhail A.,Matrosov, Anton A.,Negrebetsky, Vadim V.,Nichugovskiy, Artemiy I.,Skarga, Vladislav V.
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- Concise and efficient synthesis of linear furocoumarins: Psoralen and 4-methylpsoralen
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A method for the rapid synthesis of psoralen and 4-methylpsoralen has been developed. The key intermediates, coumarinyloxyaldehydes, were obtained in only two steps from the easily available starting materials, 7-hydroxycoumarin derivatives, by an oxidative procedure. By using Swern oxidation, psoralen and 4-methylpsoralen were finally produced in the overall yields of 71% and 67%, respectively. Copyright Taylor & Francis Group, LLC.
- Zhang, Bang-Le,Wang, Fang-Dao,Yue, Jian-Min
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- A new efficient method for the total synthesis of linear furocoumarins
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A new efficient method for the synthesis of linear furocoumarins by a Nef reaction and intramolecular cyclocondensation in one pot results in the construction of a benzofuran ring. This method provides a new strategy to furnish the benzofuran framework easily, and also allows the convenient synthesis of furocoumarin derivatives with different substituents on the coumarin ring by a subsequent Pechmann reaction. This strategy has also been applied to the preparation of four additional benzofuran derivatives. Georg Thieme Verlag Stuttgart.
- Zhang, Bang-Le,Wang, Fang-Dao,Yue, Jian-Min
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p. 567 - 570
(2007/10/03)
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- Synthesis of 2,3-dihydro-3-hydroxy-2-hydroxylalkylbenzofurans from epoxy aldehydes. One-step syntheses of brosimacutin G, vaginidiol, vaginol, smyrindiol, xanthoarnol, and avicenol A. Biomimetic syntheses of angelicin and psoralen
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(Chemical Equation Presented) We have developed two practical one-step syntheses of 2,3-dihydro-3-hydroxy-2-hydroxyalkylbenzofurans from readily available optically pure α,β-epoxy aldehydes. Electron-deficient resorcinols react with epoxy aldehydes using either Cs2CO3 in DMF or KOH/CaCl2 in MeOH to give adducts 13, 16, 18, 20, 21, and brosimacutin G (6t). Grignard reagents prepared by low-temperature halogen-metal exchange of acetoxy iodocoumarins 35d and 40 and acetoxy bromonaphthalene 41 add to epoxy aldehyde (S)-26 to complete the first syntheses of vaginidiol (7c), vaginol (7t), smyrindiol (8c), xanthoarnol (8t), and avicenol A (9t). Acid-catalyzed fragmentation of vaginidiol or vaginol provides angelicin, while that of smyrindiol or xanthoarnol affords psoralen. In both cases, the trans isomers fragment only twice as fast as the cis isomers, possibly through the intermediacy of a common benzylic cation. This may have implications for the biosynthesis of angelicin and psoralen.
- Zou, Yefen,Lobera, Mercedes,Snider, Barry B.
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p. 1761 - 1770
(2007/10/03)
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- Process for the sterilization of biological compositions and the product thereby
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The present invention concerns the product produced by inactivating extracellular or intracellular pathogenic virus in a biological composition without incurring substantial disruption or inactivation of cells and without significant loss of labile proteins or other valuable biological components also contained therein, the inactivation process comprising subjecting said composition to a virucidally effective amount of irradiation in the presence of (a) a mixture of a compound that quenches type I photodynamic reactions and a compound that quenches type II photodynamic reactions or (b) a bifunctional compound that is capable of quenching both type I and type II reactions, to thereby inactivate said virus while retaining functionality of said composition. The composition is advantageously subjected to the irradiation and the mixture of compounds or bifunctional compound in the presence of an irradiation sensitizer. Moreover, the process can be advantageously combined with a different virucidal method to enhance virus inactivation.
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- A convenient synthesis of psoralens
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An efficient synthesis (yields >70%) of linear 7H-furo[3,2-g]chromen-7-one derivatives (psoralens or furocoumarins) has been carried out starting from ring-substituted 2-(coumarin-7-yl)oxyaldehydes; moreover, the phototoxicity of these compounds has been tested on a cultured cell line of murine fibroblast.
- Chimichi, Stefano,Boccalini, Marco,Cosimelli, Barbara,Viola, Giampietro,Vedaldi, Daniela,Dall'Acqua, Francesco
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p. 4859 - 4863
(2007/10/03)
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- Coumarins from Ferulago capillaris and F. brachyloba
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Four new coumarins, (+)-senecioylprangol, (-)-3'-senecioyloxymarmesin, (+)-3'-hydroxyprantschimgin and (+)-2''-senecioyloxymarmesin, besides 12 known coumarins have been isolated from two Ferulago species. Their structures have been established by spectroscopic methods and partial synthesis. New synthetic 3'-oxocoumarins are also described. There is a remarkable difference in the contents of the most abundant coumarins found in the roots of both species: osthol and aurapten are specific to F. capillaris and F. brachyloba, respectively. (C) 2000 Elsevier Science Ltd.
- Jimenez, Benedicto,Grande, Maria Concepcion,Anaya, Josefa,Torres, Pascual,Grande, Manuel
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p. 1025 - 1031
(2007/10/03)
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- Process for the sterilization of biological compositions using UVA1 irradiation
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An improvement in a process for inactivating extracellular and intracellular viruses in a platelet containing composition is presented. The improvement in the process comprises adding a sensitizer to the platelet containing composition and irradiating the composition containing the sensitizer with UVA1 in the absence of UVA2 for a period of time sufficient to inactivate the viruses while retaining the functionality of the platelet containing composition. A quencher or mixture of quenchers of type I and type II photodynamic reactions may be advantageously added to the composition prior to irradiation.
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- Reduced and quaternized psoralens as photo-activated therapeutics
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The invention features phototherapeutic compositions comprising Type 1, Type 2, or Type 3 psoralens and methods of using such compounds for treatment of proliferative diseases of skin, blood and bone marrow.
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- Treatment methods for lymes disease and associated debilitating conditions
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A method is provided for treating human patients who have Lymes disease by using a psoralen compound, preferably administered in a dosage of 0.3 to 0.7 mg/kg, and activating same either in vitro or in vivo using electromagnetic radiation of a prescribed activating wavelength. The activation of the psoralen compound in the presence of a blood fraction from a patient suffering from Lymes disease produces a composition which will stimulate an effective immune response to the Lymes disease on the part of the patient.
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- Photodynamic inactivation of viruses in cell-containing compositions
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The present invention concerns the product produced by inactivating extracellular lipid enveloped pathogenic virus or intracellular pathogenic virus in a composition containing >1×109 cells/ml and said virus without incurring substantial disruption or inactivation of such cells, the inactivation process comprising contacting the composition with a virucidally effective amount of at least one photoreactive compound having an absorption maximum of ≥630 nm, light and an oxidizer, thereby substantially to inactivate the virus with retention of cell functionality, greater than 80%. The present invention also concerns the product produced by inactivating virus in a biological composition without incurring substantial disruption or inactivation thereof, the inactivation process comprising contacting said composition with a virucidally effective amount of at least one photoreactive compound, light, and a quencher thereby to inactivate said virus while retaining functionality of said substance.
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- An efficient synthesis of furanocoumarins
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An efficient synthesis of linear and angular furanocoumarins has been carried out starting from iodoumbelliferone derivatives. First synthesis of 6-iodoumbelliferone is described. The average yields are higher than those reported before.
- Zubia,Luis,Massanet,Collado
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p. 4239 - 4246
(2007/10/02)
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- Treatment methods and vaccines for stimulating an immunological response against retroviruses
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Human Immunodeficiency Virus infections, particularly AIDS, are treated by administering a psoralen compound which is subsequently activated by exposure to electromagnetic radiation (e.g. UVA light) whereby the activated psoralen compound attacks free virus and/or virus infected cells in the blood of the patient. The treated blood when presented to the patient's immune system engenders an effective immune response against the infection. The method has particular utility in the treatment of ARC patients who have depressed immune function.
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- STUDIES ON RUTACEANE: PART VII - AN INTERESTING REARRANGEMENT OF THE RARE EPOXYCOUMARIN. MICROMELUMIN, TO THE LINEAR FURANOCOUMARIN, PSORALEN
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Boron terifluoride etherate treatment of 7-methoxy-6-γ-butyrolactone-3'-methyl-3',4'-epoxycoumarin (micromelumin), a consistuent of Micromelum pubescens Blume (Rutaceae), afforded an interesting rearranged product, psoralen, in addition to 7-methoxycoumarinyl-6-tetronic acid derivative.
- Banerji, Julie,Das, Anup K.,Das, Biswanath
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p. 2871 - 2875
(2007/10/02)
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- Novel Bicycloannulation via Tandem Vinylation and Intramolecular Diels-Alder Reaction of Five-Membered Heterocycles: A New Approach to Construction of Psoralen and Azapsoralen
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trans-4-(Phenylsulfinyl)-3-buten-2-one (1) was found to undergo a new versatile addition-elimination reaction with five-membered compounds such as furans, pyrroles, imidazole, pyrazole, and 6-(dimethylamino)fulvene to give an excellent yield of the corresponding trans-4-aryl-3-buten-2-ones (3).The thermal reaction of the propargyl ethers 7a,b prepared from 3a,b gave a single intramolecular Diels-Alder adduct, 8a,b, in 59percent and 38percent yields, respectively.Treatment of 7a,b with t-BuOK in refluxing tert-butyl alcohol afforded another type of Diels-Alder adduct, 10a,b, in almost quantitative yields.This bicycloannulation strategy was applied to a new synthesis of psoralen which is of current interest due to its unique photoreactivity with DNA.The acid-catalyzed reaction of sulfoxide 12, prepared from ethyl acatoacetate in high yield, with furan gave 13 in 78percent yield.The intramolecular Diels-Alder reaction of the neopentyl acetal of 13 in the presence of Pd/C followed by acid hydrolysis afforded the tricyclic ketone 18 in 38percent yield.Baeyer-Villiger oxidation and dehydrogenation of 18 completed the synthesis of psoralen (11).Furthermore, hitherto unknown azapsoralen 20 was also synthesized by this method.
- Hayakawa, Kenji,Yodo, Mitsuaki,Ohsuki, Satoru,Kanematsu, Ken
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p. 6735 - 6740
(2007/10/02)
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- A Convenient Synthesis of Psoralen Derivatives: Psoralen, 4-Methyl-psoralen and 4-Phenyl-psoralen
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A convenient synthesis of psoralen derivatives, viz., 7H-furo benzopyran-7-one (psoralen), 5-methyl-7H-furo benzopyran-7-one (4-methyl-psoralen) and 5-phenyl-7H-furo benzopyran-7-one (4-phenyl-psoralen) by blocking the 8-position of the starting compounds with iodine, subsequent Claisen migration followed by cyclisation is described. - Keywords: Claisen migration; Coumarins; Psoralen derivatives
- Ahluwalia, V.K.,Prakash, Chandra,Bala, Shashi
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p. 877 - 882
(2007/10/02)
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- Method of preparing furocoumarins
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This invention relates to an improved method of preparing furocoumarins having the following formula: STR1 wherein R is a radical selected from the group consisting of hydrogen, hydroxy and lower alkoxy, which comprises reacting a coumarin having the following formula: STR2 or the alkali metal salt thereof, with a haloacetal having the following formula: STR3 WHEREIN R1 is a lower alkyl group and Hal is selected from the group consisting of chlorine and bromine; and to the intermediate products thereof, namely a substituted coumarin acetal of the following formula: STR4 and the corresponding coumarin aldehyde of the following formula: STR5
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