- Solubilization, Micellization, and Phase Equilibria of Polyoxyethylene Derivatives of Dehydroabietic Acid
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Poly(oxyethylene)dehydroabietates (DeHAb(EtO)n) with polyoxyethylene chains of 11 and 22 units have been synthesized.Phase diagrams for the systems DeHAb(EtO)11-decanol-H2O and DeHAb(EtO)22-decanol-H2O have been determined.In both systems a lamellar liquid crystalline phase is formed.The surfactants behave similarly to nonionic surfactants with an alkyl or alkyl/aryl hydrocarbon chain.The solubilization of dehydroabietinol (I), 1-octadecanol (II), decahydronaphthalene (III), decane (IV), and octadecane (V) was investigated at 60 deg C in solutions of DeHAb(EtO)22 and compared with a technical polyoxyethylene nonylphenol ether with 20 EtO units.The maximum solubilization in micellar solutions decreased in the order I > II > III > IV ca.V ca. 0 for both surfactants.These results can be conveniently correlated with the location of the solubilizates in the micelles as predicted on the basis of polarities and partial molar volumes.In all cases larger amounts were solubilized in DeHAb(EtO)22 than in the nonylphenol surfactant.This can be rationalized as a result of the lower cloud point of the DeHAb(EtO)22, which is probably due to the differences in the hydrocarbon moieties of the two surfactants.
- Persson, Margareta,Stenius, Per,Stroem, Goeran,Oedberg, Lars,Bolmgren, Ingmari,et al.
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- Synthesis of bodinieric acids A and B, both C-18 and C-19-functionalized abietane diterpenoids: DFT study of the key aldol reaction
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The first synthesis of C-18- and C-19-bifunctionalized abietane diterpenoids, bodinieric (or callicapoic) acids, via an aldol reaction has been developed. This key aldol reaction was very sensitive to steric hindrance. This fact has been studied by deuterium exchange experiments and DFT methods. Optimization of this reaction led to the synthesis of anti-inflammatory bodinieric acids A and B, starting from abietic acid.
- González-Cardenete, Miguel A.,Zaragozá, Ramón J.
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p. 15015 - 15022
(2020/04/27)
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- Antifungal Application of Rosin Derivatives from Renewable Pine Resin in Crop Protection
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In the current work, we synthesized two series of dehydroabietyl amide derivatives from natural product rosin and evaluated their antifungal effects on Valsa mali, Phytophthora capsici, Botrytis cinerea, Sclerotinia sclerotiorum, and Fusarium oxysporum. In vitro and in vivo antifungal activities results indicated that rosin-based amide compounds containing thiophene heterocycles had better inhibitory effects on B. cinerea. In particular, compound 5b (5-fluoro-2-thiophene dehydroabietyl amide) exhibited the excellent antifungal properties against B. cinerea with an EC50 of 0.490 mg/L, which was lower compared to the positive control penthiopyrad (0.562 mg/L). Physiological and biochemical studies showed that the primary action mechanism of compound 5b on B. cinerea changes mycelial morphology, increases cell membrane permeability, and inhibits the TCA pathway in respiratory metabolism. Furthermore, QSAR and SAR studies revealed that charge distribution of rosin-based amides derivatives have a key role in the antifungal activity through the hydrogen bonding, conjugation, and electrostatic interaction between the compounds and the receptors of the target. To sum up, this study contributes to the development of rosin-based antifungal agents with a novel structure and preferable biological activity.
- Gao, Yanqing,Hao, Jin,He, Xiaohua,Li, Jian,Shang, Shibin,Song, Jie,Song, Zhanqian,Tao, Pan,Wu, Chengyu
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p. 4144 - 4154
(2020/04/30)
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- Late-stage C-H amination of abietane diterpenoids
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This study aims at highlighting the synthetic versatility of the rhodium-catalyzed C-H amination reactions using iodine(iii) oxidants for the late-stage functionalization of natural products. Inter-and intramolecular nitrene insertions have been performed from various abietane diterpenoids, leading to the amination of the C-3, C-6, C-7, C-11 and C-15 positions. Ca. 20 aminated compounds have been isolated with yields of up to 86% and high levels of regio-, chemo-and stereoselectivities.
- Lapuh, María Ivana,Dana, Alejandro,Di Chenna, Pablo H.,Darses, Benjamin,Durán, Fernando J.,Dauban, Philippe
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supporting information
p. 4736 - 4746
(2019/05/24)
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- Useful catalytic enantioselective cationic double annulation reactions initiated at an internal π-bond: Method and applications
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The 1:1 complex of o,o'-dichloro-R-BINOL and SbCl5 initiates the enantioselective cationic polycyclization of polyunsaturated substrates at a predictable π-bond which may be either terminal or, as shown herein, internal. The extension of this powerful construction to internal π-bonds expands the scope of this method and opens up very short pathways to numerous chiral polycyclic molecules, including natural products and their analogues. Especially simple synthetic routes are disclosed that provide access to dysideapalaunic acid, dehydroabietic acid, and epipodocarpic acid and illustrate the value of this enantioselective approach.
- Surendra, Karavadhi,Rajendar, Goreti,Corey
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p. 642 - 645
(2014/02/14)
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- Syntheses of taiwaniaquinone F and taiwaniaquinol A via an unusual remote C-H functionalization
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A protecting-group-free route to (-)-taiwaniaquinone F based on a ring contraction and subsequent aromatic oxidation of a sugiol derivative is reported. In addition, the first synthesis of (+)-taiwaniaquinol A is reported via short time exposure of (-)-taiwaniaquinone F to sunlight triggering a remote C-H functionalization. The hypothesis that the biogenesis of some methylenedioxy bridged natural products could proceed via similar nonenzymatic mechanisms is presented.
- Thommen, Christophe,Jana, Chandan Kumar,Neuburger, Markus,Gademann, Karl
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supporting information
p. 1390 - 1393
(2013/04/24)
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- Synthesis and biological evaluation of dehydroabietic acid derivatives
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A series of C18-oxygenated derivatives of dehydroabietic acid were synthesized from commercial abietic acid and evaluated for their cytotoxic, antimycotic, and antiviral activities.
- Gonzalez, Miguel A.,Perez-Guaita, David,Correa-Royero, Julieth,Zapata, Bibiana,Agudelo, Lee,Mesa-Arango, Ana,Betancur-Galvis, Liliana
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experimental part
p. 811 - 816
(2010/04/26)
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- Dimethylaluminum methyltellurate, a new reagent for the cleavage of hindered methyl esters under exceptionally mild conditions by a novel mechanism
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An efficient and effective new reagent (Me2AlTeMe)2 has been developed for the conversion of methyl esters to the corresponding carboxylic acids in toluene solution at 23°C.
- Reddy, B.V. Subba,Reddy, Leleti Rajender,Corey
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p. 4589 - 4593
(2007/10/03)
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- An efficient, stereocontrolled synthesis of a potent omuralide-salinosporin hybrid for selective proteasome inhibition
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A short and highly stereocontrolled synthesis of the potent proteasome inhibitor 3 from the (S)-threonine-derived oxazoline 4 has been developed. The synthetic sequence is summarized in Scheme 1. Aldol coupling of the zinc enolate of 4 with isobutyraldehyde and subsequent silylation provided the TBS ether 5 diastereoselectively (10:1). Reductive cleavage of the oxazoline ring of 5 followed by Swern oxidation of the resulting amino alcohol afforded amino ketone 6, converted further by N-acylation to the acrylamide 7, whose structure was confirmed by X-ray crystallographic analysis. Acrylamide 7 was cyclized to 8 by a novel application of the Kulinkovich Ti(II)-cyclopentene complex. Silylation of 8 to 9 and radical cyclization at low temperature produced the bicyclic lactam 10 with complete control of all stereocenters. Hydroxy desilylation and N-deprotection of 10 gave the dihydroxy ester 11, which was converted to 3 by a novel three-step sequence: (1) demethylation with [Me2AlTeMe]2, (2) combined β-lactonization and chlorination, and (3) desilylation to effect cleavage of the TBS ether. Copyright
- Reddy, Leleti Rajender,Fournier, Jean-Francois,Reddy, B. V. Subba,Corey
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p. 8974 - 8976
(2007/10/03)
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- Oxonitriles: Multicomponent Grignard addition-alkylations
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Three at a time: Sequential carbonyl addition, chelation-controlled conjugate addition, and alkylation triggers the multicomponent assembly of diverse nitriles. The chelation-controlled conjugate addition-alkylation installs three new stereocenters (see scheme), thereby generating substituted nitriles that are ideal terpenoid precursors as illustrated in the synthesis of epi-dehydroabietic acid.
- Fleming, Fraser F.,Zhang, Zhiyu,Wang, Qunzhao,Steward, Omar W.
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p. 1126 - 1129
(2007/10/03)
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- Sulphonated dehydrogenated sylvate, the preparation and use
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This invention relates to salts of sulfodehydroabietic acid with bismuth or zinc, a kind of new salt useful in treating digestive canal ulcer, acute and chronic gastritis, and erosive gastritis etc., as well as its preparation and use. Said salts can be represented by formula (1), wherein R is Bi(OH)++ or Zn++, 2Bio+, 1/2ZnH, n=0-10. The preparation method comprises following steps: (a) sequentially treating the industrial abietic acid calcium salt with acid, base and extracting with organic solvent to give abietic acid with less isomer; (b) reacting said abietic acid with Pd/C to provide dehydroabietic acid, then converting it to pure sulphonic product, namely sulfodehydroabietic acid, via sulphonation and recrystallization; (c) by use of neutralization or salt displacement reaction to convert the sulphonic product of zinc or bismuth salts of sulfodehydroabietic acid. The resultant salts can used to prepare medicine for treating digestive canal ulcer and gastritis.
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Page/Page column 5-6
(2008/06/13)
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- Inhibition of platelet aggregation by diterpene acids from Pinus massoniana resin
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The acidic fraction of the resin of Pinus massoniana Lamb. from China was converted to the p-nitrophenyl esters, and the esters separated by chromatography. The separated p-nitrophenyl esters were individually hydrolysed by potassium hydroxide in acetone-water at room temperature to 8 diterpene acids of the pimarane and abietane groups: pimaric acid (8(14),15-pimaradien-18-oic acid) (1), levopimaric acid (8(14),12-abietadien-18-oic acid (2), palustric acid (8,13-abietadien-18-oic acid) (3), neoabietic acid (8(14),13(15)-abietadien-18-oic acid) (4), abietic acid (7,13-abietadien-18-oic acid) (5), dehydroabietic acid (8,11,13-abietatrien-18-oic acid) (6), 7-oxodehydroabietic acid (7-oxo-8,11,13-abietatrien-18-oic acid) (7) and 7α-hydroxydehydroabietic acid (7α-hydroxy-8,11,13-abietatrien-18-oic acid) (8). The structure (and stereochemistry) of the diterpene acids were substantiated by nulear magnetic resonance spectroscopy (proton and carbon-13, one and two dimensional), by mass spectrometry (electron impact and methane chemical ionization) and by rotation measurements. The 8 diterpene acids were tested for their ability to inhibit the aggregation of washed rabbit platelets induced by platelet activating factor (PAF), adenosine diphosphate (ADP) and by calcium ionophore A23187. With platelet aggregation induced by the latter two agonists, activities comparable with or higher than linolenic acid were given by the first 4 acids. With aggregation induced by PAF, the first 3 acids show activity, but at a level significantly lower than that of linolenic acid. Levopimaric acid has the highest activity among the diterpene acids tested. It is proposed that this activity is related to the folded shape of the molecule.
- Cheung,Fu,Smal
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- RETRODIENE CLEAVAGE OF DIENE ADDUCTS OF LEVOPIMARIC ACID AS A PATH TO THE SYNTHESIS OF DERIVATIVES OF TERPENOID NAPHTHO- AND ANTHRAQUINONES
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The -cycloaddition of benzo- and naphthoquinones to levopimaric acid was investigated, and the retrodiene cleavage of the adducts was realized.The prospects of such a method in the synthesis of the analogs of natural terpenoid quinones, which are of interest as bioregulators, were demonstrated.
- Tolstikov, G. A.,Shul'ts, E. E.,Mukhametzyanova, T. Sh.,Baikova, I. P.,Spirikhin, L. V.
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p. 585 - 598
(2007/10/02)
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- Investigation of the Allergenic Principles from Colophony: Autoxidation, Synthesis, and Sensitization
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The autoxidation of abietic acid (1a), levopimaric acid (2a), and dehydroabietic acid (3a) was studied and the compounds 3a as well as (after esterification) 8b, 9b, 10b, 11b (from 1a); 6b (from 2a); and 4b, 5b (from 3a) were isolated for the first time.Some derivatives (6a, 6b, 13b/14b, and 7b) were semi-synthezised.The isolated autoxidation products, the synthetic compounds and some polar fractions of natural colophony were tested for their sensitizing capacity.Compounds 4a, 10b, 16, and 18 as well as the combined polar fraction A-D of colophony show enhanced sensitizing capacity.Methylation of the acids to the ester significantly reduces their activity.Key Words: Resin acids, autoxidation of / Colophony, allergy of / Sensitizing potency
- Krohn, Karsten,Budianto, Emil,Floerke, Ulrich,Hausen, Bjoern M.
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p. 911 - 920
(2007/10/02)
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