- Dual Nickel/Ruthenium Strategy for Photoinduced Decarboxylative Cross-Coupling of α,β-Unsaturated Carboxylic Acids with Cycloketone Oxime Esters
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Herein, a dual nickel/ruthenium strategy is developed for photoinduced decarboxylative cross-coupling between α,β-unsaturated carboxylic acids and cycloketone oxime esters. The reaction mechanism is distinct from previous photoinduced decarboxylation of α,β-unsaturated carboxylic acids. This reaction might proceed through a nickelacyclopropane intermediate. The C(sp2)-C(sp3) bond constructed by the aforementioned reaction provides an efficient approach to obtaining various cyanoalkyl alkenes, which are synthetically valuable organic skeletons in organic and medicinal chemistry, under mild reaction conditions. The protocol tolerates many critical functional groups and provides a route for the modification of complex organic molecules.
- Gao, Ang,Jiang, Run-Chuang,Liu, Chuang-Chuang,Liu, Qi-Le,Lu, Xiao-Yu,Xia, Ze-Jie
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p. 8829 - 8842
(2021/06/30)
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- Novel isomerization method of acitretin
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The invention belongs to the field of drug synthesis and research, and particularly relates to an isomerization catalyst which is a palladium-carbon composite catalyst and is a mixture of palladium-carbon and triphenylphosphine, and the molar ratio of the palladium-carbon to the triphenylphosphine is 1 to (1-10). The invention further provides a novel isomerization method of acitretin. The isomerization catalyst is adopted to perform an isomerization reaction, so that an isomer 11-cis,13-trans-acitretin in the mixture can be effectively converted into a medicinal all-trans acitretin, materialwaste is avoided, the prepared acitretin product is high in purity, the palladium-carbon catalyst can be recovered by adopting a simple method and can be reused, the product cost is reduced, the concentration of heavy metal ions in wastewater is low, the environmental pollution is reduced, and the process is environmentally friendly.
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Paragraph 0059-0070
(2018/10/19)
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- PROCESS FOR PREPARATION OF ACITRETIN
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The present invention provides a process for preparation of {(2E,4E,6E,8E)-9-(4-methoxy-2,3,6- trimethyl)phenyl-3,7-dimethyl-nona-2,4,6,8}tetraenoate, an acitretin intermediate of formula (VI) with trans isomer ≥97%, comprising of reacting 3-formyl-crotonic acid butyl ester of formula (V), substantially free of impurities, with 5-(4-methoxy-2,3,6-trimethylphenyl)-3- methyl-penta-2,4-diene-l-triphenyl phosphonium bromide of formula (IV) and isolating resultant compound of formula (VI), treating the filtrate with iodine for isomerization of the undesired cis intermediate and finally obtaining acitretin (I), with desired trans isomer ≥97%.
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- STEREOSPECIFIC SYNTHESIS PROCESS FOR TRETINOIN COMPOUNDS
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A stereospecific synthesis process for tretinoin compounds comprises the following steps: using substituted triphenyl phosphine salt and β-formyl crotonic acid as raw material to carry out WITTIG reaction under the action of alkali; then adjusting the pH of the reaction liquid to 5-10; adding palladium compound or rhodium compound to carry out isomerization directly and obtain tretinoin compounds with desired configuration. The product yield of the process is high and the intermediate product in the reaction dose not need to be separated. The process is easy to operate and can save the production cost and as well is suitable for industrial production.
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Paragraph 0045; 0046
(2014/04/03)
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- Stereospecific synthesis process for tretinoin compounds
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A stereospecific synthesis process for tretinoin compounds comprises the following steps: using substituted triphenyl phosphine salt and β-formyl crotonic acid as raw material to carry out WITTIG reaction under the action of alkali; then adjusting the pH of the reaction liquid to 5-10; adding palladium compound or rhodium compound to carry out isomerization directly and obtain tretinoin compounds with desired configuration. The product yield of the process is high and the intermediate product in the reaction dose not need to be separated. The process is easy to operate and can save the production cost and as well is suitable for industrial production.
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Page/Page column 9; 10
(2014/09/29)
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- Syntheses, antiproliferative activity and theoretical characterization of acitretin-type retinoids with changes in the lipophilic part
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Acitretin analogs, incorporating changes in the lipophilic part, were efficiently synthesized from commercially available aromatic aldehydes or methyl ketones using the Wittig or Horner-Wadsworth-Emmons reaction. Their antiproliferative activity was evaluated against human breast MCF-7 epithelial cells. Analogs 3, 4, 8 and 11 exhibited strong, dose-dependent, antiproliferative activity on the tested cell line. Analog 3, incorporating three methoxy groups in the aromatic ring, exhibited the strongest inhibitory effect at 10 μM. High-level all electron conventional ab initio and density functional theory quantum chemical calculations were performed to obtain the molecular structure, electron charge distribution and polarization properties of all compounds of interest in this work. The most active analogs were planar and were characterized by larger dipole moments than the other synthesized molecules. Another factor of importance to the analysis of the activity of these molecules is the dipole polarizability.
- Magoulas, George E.,Bariamis, Stavros E.,Athanassopoulos, Constantinos M.,Haskopoulos, Anastasios,Dedes, Petros G.,Krokidis, Marios G.,Karamanos, Nikos K.,Kletsas, Dimitris,Papaioannou, Dionissios,Maroulis, George
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p. 721 - 737
(2011/03/20)
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- PROCESS FOR PREPARATION OF PURE ACITRETIN
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Processes and systems for the preparation of substantially pure acitretin based on reacting crude acitretin and an amine in presence of a suitable solvent to provide a salt that is then reacted with an organic acid to obtain substantially pure acitretin.
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Page/Page column 2
(2009/05/28)
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- Process for the preparation of pure acitretin
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The invention relates to a process for the preparation of substantially pure Acitretin, which comprises the following steps: a) salifying crude Acitretin with an amine of formula (II) ???????? R1R2R3N?????(II) wherein each of R1, R2 and R3 is, independently, hydrogen, a C1-C6 alkyl group, a C3-C8 cycloalkyl group, a phenyl, morpholino or pyridino group, in the presence of an alcohol or water-alcohol solvent; and b) adding an organic acid to the salt obtained in step a).
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Page/Page column 3
(2009/06/27)
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- A new stereoselective synthesis of acitretin (=Soriatane, Neotigason)
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A new synthesis of acitretin via a C15 + C5 route is reported. The C15 unit is the key step, involving a procedure that provides the required (all-E)-C15-aldehyde with high stereoselectivity.
- Andriamialisoa, Zo,Valla, Alain,Cartier, Dominique,Labia, Roger
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p. 2926 - 2929
(2007/10/03)
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- Stable acitretinoid compounds
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Novel acitretinamide compounds which are soluble and stable in water and useful in aqueous delivery systems, particularly to treat cancer, are provided. The novel acitretinamide compounds, 1-(D-glucopyranosyl)acitretinamide, 1-(D-glucopyranuronosyl)acitretinamide and the metal salts thereof, are hereinafter collectively referred to as the "acitretinamide compounds". The invention also relates to novel methods of making the acitretinamide compounds.
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- Trienediolates of hexadienoic acids in synthesis. Addition to unsaturated ketones. A convergent approach to the synthesis of retinoic acids
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The regioselectivity of the addition of the lithium trienediolates generated from hexa-2,4-dienoic acids 1 and 2 or the dihydropyran-2-ones 4 and 5 to unsaturated ketones 6 is studied. Equilibration conditions favour reaction of the trienediolates through their ω carbon, and the ketones according to 1,2- and 1,4-additions. β-Ionone 6a and the aryl-butenone 6b lead to the 1,2-ω-adducts 8, which undergo a facile acid catalyzed dehydration to retinoic acids 11. On reaction with the unsaturated ketone 6b or with the aryl ketones 21, the trimethyldihydropyran-2-one 5 leads to γ'-adducts derived from deprotonation of the chain methyl substituent along with the 1,4-ω-adducts.
- Aurell, Maria J.,Ceita, Luisa,Mestres, Ramon,Parra, Margarita,Tortajada, Amparo
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p. 3915 - 3928
(2007/10/02)
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- Glutathione catalysis of interconversion of acitretin and its 13-cis isomer isoacitretin
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The ability of glutathione to catalyze the cis-trans isomerization of acitretin and isoacitretin was explored. Glutathione catalyzed the isomerization reaction in both directions; the reaction rate varied with glutathione concentration, atmospheric exposure condition, and identity of starting isomer. The ability of this widely distributed molecule to catalyze this interconversion nonenzymatically may contribute to the presence of both isomers in vivo after administration of either isomer.
- Jewell,McNamara
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p. 444 - 446
(2007/10/02)
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- STEREOSELECTIVE SYNTHESIS OF THE AROMATIC ANALOGS OF RETINAL AND RETONOIC ACID
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The stereoselective synthesis of 9-aryl-4-carboxy-3,7-dimethyl-2Z,4Z,6E,8E-nonatetraenoic acids and 9-aryl-3,7-dimethyl-2Z,4E,6E,8E-nonatetraenoic acids was realized.The latter isomerize readily and with good yields under the influence of iodine additions to 9-aryl-3,7-dimethyl-2E,4E,6E,8E-nonatetraenoic acids.The transition from the isomeric 9-aryl-3,7-dimethyl-2,4,6,8-nonatetraenoic acids to the corresponding isomeric 9-aryl-3,7-dimethyl-2Z,4E,6E,8E-nonatetraenals and 9-aryl-3,7-dimethyl-2E,4E,6E,8E-nonatetraenals was realized.
- Makin, S. M.,Mikerin, I. E.,Shavrygina, O. A.,Lanina, T. I.
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p. 710 - 715
(2007/10/02)
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- 9-Phenyl-nonate traene compounds
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Novel 9-phenyl 5,6-dimethyl-nona-2,4,6,8-tetraenoic acid, tetraenal or tetraenol derivatives useful as anti-tumor agents.
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- Antidandruff compositions containing 9-(4-lower alkoxy-2,3,6-trilower-alkylphenyl)-3,7-dimethyl-nona-2,4,6,8-tetraen-1-oic acid lower alkyl amides
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Compositions suitable for the care of the hair and scalp particularly with respect to the control of dandruff are disclosed. Said compositions comprise a suitable inert carrier and, as an active ingredient, a compound selected from those represented by the formula STR1 wherein R1, R2, R3, R4 and R6 are lower alkyl.
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