- ALISMOL AND ALISMOXIDE, SESQUITERPENOIDS OF ALISMA RHIZOMES
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From the crude drug 'takusha', wich is the rhizomes of Alisma plantago-aquatica var. orientale, two new sesquiterpenoids, alismol and alismoxide, have been isolated.Their structures have been estabished on the basis of chemical and physical evidence to be 1β,5β-guaia-6,10(15)-dien-4-ol and 4,10-epoxy-1β,5β-guaia-6-ene, respectively. - Key Word Index: Alisma plantago-aquatica var. orientale; Alismataceae; sesquiterpenoid; guaiane skeleton; alismol; 1β,5β-guaia-6,10(15)-dien-4-ol; alismoxide; 4,10-epoxy-1β,5β-guaia-6-ene
- Oshima, Yoshiteru,Iwakawa, Tsuneo,Hikino, Hiroshi
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- Reaction of azulene with 1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol in a mixed solvent of methanol and acetonitrile in the presence of hydrochloric acid: A facile one-pot synthesis and properties of new triarylethylenes possessing an azulen-1-yl group
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Reaction of azulene (1) with 1,2-bis[4-(dimethylamino)phenyl]-1,2- ethanediol (2) in a mixed solvent of methanol and acetonitrile in the presence of 36% hydrochloric acid at 60 °C for 3 h gives 2-(azulen-1-yl)-1,1-bis[4- (dimethylamino)phenyl]ethylene (3) (8% yield), 1-(azulen-1-yl)-(E)-1,2-bis[4- (dimethylamino)phenyl]ethylene (4) (28% yield), and 1,3-bis{2,2-bis[4- (dimethylamino)phenyl]ethenyl}azulene (5) (9% yield). Besides the above products, this reaction affords 1,1-di(azulen-1-yl)-2,2-bis[4-(dimethylamino) phenyl]ethane (6) (15% yield), a meso form (1R,2S)-1,2-di(azulen-1-yl)-1,2- bis[4-(dimethylamino)phenyl]ethane (7) (6% yield), and the two enantiomeric forms (1R,2R)- and (1S,2S)-1,2-di(azulen-1-yl)-1,2-bis[4-(dimethylamino)phenyl] ethanes (8) (6% yield). Furthermore, addition reaction of 3 with 1 under the same reaction conditions as the above provides 6, in 46% yield, which upon oxidation with DDQ (=2,3-dichloro-5,6-dicyano-1,4-benzoquinone) in dichloromethane at 25 °C for 24 h yields 1,1-di(azulen-1-yl)-2,2-bis[4- (dimethylamino)phenyl]ethylene (9) in 48% yield. Interestingly, reaction of 1,1-bis[4-(dimethylamino)phenyl]-2-(3-guaiazulenyl)ethylene (11) with 1 in a mixed solvent of methanol and acetonitrile in the presence of 36% hydrochloric acid at 60 °C for 3 h gives guaiazulene (10) and 3, owing to the replacement of a guaiazulen-3-yl group by an azulen-1-yl group, in 91 and 46% yields together with 5 (19% yield) and 6 (13% yield). Similarly, reactions of 2-(3-guaiazulenyl)-1,1-bis(4-methoxyphenyl)ethylene (12) and 1,1-bis{4-[2-(dimethylamino)ethoxy]phenyl}-2-(3-guaiazulenyl)ethylene (13) with 1 under the same reaction conditions as the above provide 10, 2-(azulen-1-yl)-1,1-bis(4-methoxyphenyl)ethylene (16), and 1,3-bis[2,2-bis(4- methoxyphenyl)ethenyl]azulene (17) (93, 34, and 19% yields) from 12 and 10 and 2-(azulen-1-yl)-1,1-bis{4-[2-(dimethylamino)ethoxy]phenyl}ethylene (18) (97 and 58% yields) from 13.
- Takekuma, Shin-Ichi,Kaibara, Masamichi,Minematsu, Toshie,Takekuma, Hideko
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experimental part
p. 4780 - 4792
(2011/08/03)
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- Approach to the blues: A highly flexible route to the azulenes
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(Chemical Equation Presented) A palette of blues: Chlorobicyclo-[5.3.0] decatrienones are readily prepared from cycloheptatrienes by cycloaddition of dichloroketene, ring expansion with a diazoalkane, and dehydrochlorination in dimethylformamide. These compounds are used as intermediates in the regiocontrolled synthesis of a wide variety of natural and nonnatural azulenes (see scheme).
- Carret, Sebastien,Blanc, Aurelien,Coquerel, Yoann,Berthod, Mikael,Greene, Andrew E.,Depres, Jean-Pierre
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p. 5130 - 5133
(2007/10/03)
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- Chemistry of (+)-aromadendrene. Part 6: Rearrangement reactions of ledene, isoledene and their epoxides
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The chemistry of (+)-ledene and (-)-isoledene, both easily available from (+)-aromadendrene has been investigated. Reactions at the double bond of ledene take place preferably from the β-side. Under acidic conditions its C7-C8 β-epoxide and β-diol preferably react via carbocations, which are initially formed at C8. Rearrangement takes place to compounds with cubebane and cadinane skeletons. The reaction pattern of isoledene and its α-epoxide, under acidic conditions, is governed by the easy formation of an intermediate α-cyclopropylcarbinyl carbocation. Further reactions lead to products in which the C2-C3 bond of the cyclopropane ring is broken to give compounds with a guaiane skeleton. Guaiane-type dienes and unsaturated cyclic ethers are the final products of these rearrangements. Several derivatives of these compounds have been prepared.
- Moreno-Dorado, F. Javier,Lamers, Yvonne M. A. W.,Mironov, Grigore,Wijnberg, Joannes B. P. A.,De Groot, Aede
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p. 7743 - 7750
(2007/10/03)
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- Reaction of Guaiazulene with Bromine in Hexane and in Aqueous Tetrahydrofuran
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2-Bromoguaiazulenium bromide and 3,3-dibromo guaiazulenium bromide were obtained respectively from the reaction of guaiazulene and its 3-bromo compound with 1 equivalent of bromine in hexane at -20 deg C.The former compound afforded in methanol a mixture of guaiazulene, 3,3'-biguaiazulene, and oligomers, and gave 3-bromoguiazulene quantitatively with alkali.Dibromoguiazulenium bromide afforded with further moles of bromine in aqueous THF a mixture of guaiazulenequinone, 3-bromo-1-hydroxyquaiazulen-5-one, and a dark blue solid A in different ratios depending on the reaction conditions.
- Nozoe, Tetsuo,Shindo, Kimio,Wakabayashi, Hidetsugu,Kurihara, Teruo,Uzawa, Jun
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p. 687 - 688
(2007/10/02)
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- Formation and Thermal Rearrangement of Dimethyl Tricyclo1,7>dodeca-2,4,6,9,11-pentaene-9,10-dicarboxylates
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The high-pressure reaction of 1-methylazulenes 1 with excess of dimethyl acetylenedicarboxylate (ADM) in hexane at 30 deg and at pressures up to 7 kbar affords the tricyclic compounds 2 in reasonable-to-good yields (cf.Table 1).The crystalline compounds 2 decompose on melting into the starting materials and undergo rearrangement to the corresponding heptalene-1,2-dicarboxylates 6.The X-ray crystal-structure analyses of 2f and 2g (cf.Fig. 1) reveal the presence of a perfectly planar seven-membered ring and comparably long C(1)-C(10) as well as C(1)-C(11) bonds (cf.Tables 2 and 3).The thermolysis of 2g in different solvents leads in aprotic media to the formation of the starting azulene 1g and, depending upon the polarity of the solvents, to varying amounts of the corresponding heptalene-1,2-dicarboxylate 6f (cf.Table 11).The formed amounts of 1g depends linearly on the ET values of the solvents (cf.Fig. 4).The same is valid for the thermolysis of 2g in protic media (cf.Table 10 and Fig. 3).However, in these cases instead of the heptalene-1,2-dicarboxylate 6g, the corresponding (E)- and (Z)-isomers of the 1-(azulen-1-yl)ethene-1,2-dicarboxylates 7g are formed.The other tricyclic compounds 2 exhibit the same behavior on thermolysis in MeCN and BuOH (cf.Tables 8 and 9, resp.).The results show that the tricyclic compounds 2 undergo at temperatures up to 110 deg C two competing reactions, namely heterolysis of the C(1)-C(10) bond, leading to the formation of heptalenes 6 in polar aprotic media, and (E)- and (Z)-ethene-1,2-dicarboxylates 7 in polar protic media, and concerted homolysis of the C(1)-C(10) and C(8)-C(9) bonds in the sense of a retro-Diels-Alder reaction in apolar media, yielding the starting azulenes and ADM, the amount of which decrease with increasing polarity of the solvent.The kinetic and activation parameters measured for 2g and the other tricyclic compounds 2 are collected in Tables 12-15.The tricyclic compounds 2a and 2b show in polar aprotic media (MeCN) a different behavior in that they form, instead of heptalenes, the corresponding 3,4-dihydrocyclopentazulene-1,2-dicarboxylates 16a and 16b, respectively (Scheme 4).Experiments with -2a showed that these compounds are not formed via intramolecular H-shifts (cf.Schemes 8 and 9).
- Fallahpour, Reza-Ali,Hansen, Hans-Juergen
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p. 1933 - 1970
(2007/10/02)
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- Novel Dimerization of 3-(2-Nitroethenyl)guaiazulene. A Convenient Route to Cyclopentaheptalene
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Dimerization of 3-(2-nitroethenyl)guaiazulene with sodium methylate gave 5-(1-guaiazulenyl)-5,6-dihydro-9-isopropyl-1-methyl-4-nitrocyclopentahepatalene (3).On treatment with formic acid, 3 was converted into 9-isopropyl-1-methyl-4-nitrocyclopentaheptalene quantitatively.A combination of the reactions provides a convenient route to the cyclopentaheptalene derivatives.
- Kurokawa, Shinji
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p. 1109 - 1112
(2007/10/02)
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- Acid-catalyzed Ethanolysis of Di-1-azulenyl Ketones
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Substituted di-1-azulenyl ketones composed of 3,8-dimethyl-5-isopropyl-1-azulenyl and/or 4,6,8-trimethyl-1-azulenyl group were refluxed in ethanol in the presence of p-toluenesulfonic acid to give substituted azulenes and ethyl azulene-1-carboxylates derived from the cleavage of either of C-CO bonds of di-1-azulenyl ketones.The facility and the product distributions of the ethanolysis were affected markedly by the substitutents.
- Saitoh, Masaki,Hashimoto, Keitaro,Nakazawa, Tomoo,Sugihara, Yoshikazu
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p. 3563 - 3566
(2007/10/02)
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- Azulenic retinoid compounds, compositions and methods
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Novel azulenic retinoid compounds and therapeutic compositions are disclosed, along with method for their production and use as anti-cancer and cancer-prevention agents. The compositions of the present invention will also find use in treating dermatological disorders such as acne and psoriasis, as well as dermatologically-related conditions such as repair and effacement of wrinkles.
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- Electroorganic Chemistry. 140. Electroreductively Intra- and Intermolecular Couplings of Ketones with Nitriles
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Electroreduction of γ- and δ-cyano ketones in i-PrOH with Sn cathode gave α-hydroxy ketones and their dehydroxylated ketones as the intramolecularly coupled products.Guaiazulene, (-)-valeranone, polyquinanes, dihydrojasmone, methyl dihydrojasmonate, and rosaprostol have been synthesized by utilizing this electroreductive intramolecular coupling of γ- and δ-cyano ketones in one of the key steps.Similarly, electroreduction of a mixture of ketone and nitrile gave the corresponding intermolecularly coupled product.The product obtained by the electroreductive intermolecular coupling of (+)-dihydrocarvone with acetonitrile has been found to be the precursor of an effective chiral ligand for the enantioselective addition of diethylzinc to aldehydes.
- Shono, Tatsuya,Kise, Naoki,Fujimoto, Taku,Tominaga, Naoto,Morita, Hiroshi
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p. 7175 - 7187
(2007/10/02)
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- Facile Shifts of Bromine Atom on C-3 Position of Guaiazulene and Synthesis of Variously Functionalized Azulenes Using These Reactions
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Treatment of guaiazulene (1) with NBS in hexane gave exclusively 3-bromo compound, while in benzene it afforded various side-chain-brominated compounds.Shifts of bromine atom catalyzed by succinimide were observed in benzene, presumably via intermolecular radical pathways.Using these reactions, various side-chain-functionalyzed derivatives of 1, including epoxy compounds, were prepared.
- Nozoe, Tetsuo,Ishikawa, Sumio,Shindo, Kimio
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p. 353 - 356
(2007/10/02)
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- Sustained release pharmaceutical plaster
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A sustained release pharmaceutical plaster which is characterized in that it is a pharmaceutical preparation mainly composed of an adhesive compound layer and a supporter which supports the adhesive compound layer, inside of which there is an arrangement of hollow fibers, that have radially arranged open pores, with their tubular hollows filled with medicines.
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- 6-(3-Guaiazulenyl)-5-isopropyl-3,8-dimethyl-1(6H)-azulenone and Its Norcaradiene-Isomer. Key Intermediates for Novel Intermolecular One-Carbon Transfer in Autoxidation of Guaiazulene
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Autoxidation of guaiazulene either at 85 deg C in N,N-dimethylformamide-0.5 M sulfuric acid or at 25-35 deg C on the surface of a filter paper yielded, together with other products, the two title compounds which were shown to be in equilibrium and to constitute important intermediates for the intermolecular one-carbon transfer reactions frequently observed during autoxidation of many azulenic hydrocarbons.
- Matsubara, Yoshiharu,Takekuma, Shin-ichi,Yamamoto, Hiroshi,Nozoe, Tetsuo
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p. 455 - 458
(2007/10/02)
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- (6R,7S)-7-Amino-7,8-dihydro-α-bisabolene, an Antimicrobial Metabolite from the Marine Sponge Halichondria sp.
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The antimicrobial constitiunts of the marine sponge Halichondria sp. from Ponape have been identified as (6R,7S)-7-amino-7,8-dihydro-α-bisabolene (3) and its hydrochloride salt 4.The structure of amine 3 was determined by an X-ray crystallographic study of the corresponding symmetrical urea 5 and the absolute configuration was elucidated by chemical conversion to (6R,7e)-α-bisabolene.The urea 5, the corresponding isothiocyanate 6, and an unrelated diene 7 were also isolated from the sponge.
- Sullivan, Brian W.,Faulkner, D. John,Okamoto, Kelvin T.,Chen, Marie H. M.,Clardy, Jon
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p. 5134 - 5136
(2007/10/02)
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- STRUCTURE OF ERGOLIDE
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The epigeal part of Erigeon khorassanicus Boiss. has yielded a new sesquiterpene lactone of the pseudoguaiane type - ergolide C17H22O5, mp 179-180 deg C (ethanol) D20 +123 deg (c 4.88; ethanol).On the basis of chemical transformations and spectral chracteristics, its structure and configuration have been established as 6-acetoxy-4-oxo-1,7αH,6,8,10βH-pseudoguai-11(13)-en-8,12-olide.
- Ovezdurdyev, A.,Abdullaev, N. D.,Kasymov, Sh. Z.,Akyev, B.
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p. 532 - 535
(2007/10/02)
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