- Thermodynamic study on the effects of β-cyclodextrin inclusion with berberine
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The fluorescence enhancement of berberine (Berb) as a result of complex with β-cyclodextrin (β-CD) is investigated. The association constants of α-CD and β-CD with Berb are 60 and 137 M-1 at 20°C in pH 7.20 aqueous solution. Effects of temperature on the forming inclusion complexes of β-CD with Berb have been examined through using fluorescence titration. Enthalpy and entropy values calculated from fluorescence data are -33.7 kJ·mol-1 and 74.3 J·mol-1·K-1, respectively. It was found that the dielectric constant of β-CD cavity is about 24 in a rough analogy with absolute alcohol. These results suggest that the extrusion of 'high energy water' molecules from the cavity of β-CD and hydrophobic interaction upon the inclusion complex formation are the main forces of the inclusion reaction. Effect of pH on the association of β-CD with Berb was also studied. Mechanism of the inclusion of β-CD with Berb is further studied by absorption and NMR measurements. Results show that β-CD forms a 1:1 inclusion complex with Berb.
- Yu,Wei,Gao,Zhao
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- A synthetic preparation method for small carbags hydrochloric acid
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The present invention belongs to the field of organic chemistry, relates to a method of synthesizing berberine hydrochloride, comprising: S1: with 5-halo-o-quinoastearaldehyde and piperine ethylamine to obtain N- [2-(3,4-dimethoxyphenyl-5-yl) ethyl] -1- (5-halo-2,3-dimethoxybenzyl) methylimide; S2: to obtain 2- (3,4-diimoxyphenyl) -N- (5-bromo-2,3-dimethoxybenzyl) ethylamine; S3: to obtain 2-(3,4-dimethoxyphenyl) -N- (5-bromo-2 S4: to obtain 12-halogenated berberine derivative; S5: to obtain berberine. The present invention is free from the application of the by-product o-vanillin synthesis of o-resveratal raw material constraints, synthesis of 5- substitute o-resveratal and piperine ethylamine, and the use of the two preparation of berberine hydrochloride, with raw materials readily available, mild reaction conditions, easy to operate, high chemical yield, low cost and other advantages.
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Paragraph 0276-0286
(2021/12/08)
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- Modular and Divergent Syntheses of Protoberberine and Protonitidine Alkaloids
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A modularly convergent and divergent strategy was established for the family synthesis of both protoberberine and protonitidine alkaloids. The robust, scalable, and flexible synthetic route featured a collective preparation of protoberberine and protonitidine alkaloids from a common isoquinoline assembled from pyridyne as the key synthon, which was based on the selective N-C or C-C cyclization via distinct processes. Through the strategy, 20 protoberberine alkaloids, 5 protonitidine alkaloids, and 11 analogues with diverse substituents were comprehensively aquired.
- Liu, Kai,Jiang, Xuefeng
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p. 1327 - 1332
(2021/03/03)
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- The total synthesis of berberine and selected analogues, and their evaluation as amyloid beta aggregation inhibitors
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The total synthesis of berberine and selected analogues. And their evaluation as amyloid β (Aβ) aggregation inhibitors is described. The key step in the synthesis, the assembly of the berberine framework, was accomplished using an intermolecular Heck reaction. Berberine analog 17 incorporating a tertiary amine moiety showed good anti Aβ aggregation activity, water solubility, and almost no toxicity to nerve cells.
- Tajiri, Misato,Yamada, Ryo,Hotsumi, Mayumi,Makabe, Koki,Konno, Hiroyuki
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- The ring formation mechanism in cyclization of berberine
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Berberine hydrochloride is a natural alkaloid with significant antitumor activities against many types of cancer cells, can be synthesized by cyclic reaction with hydrochloride condensate and glyoxal as raw materials and copper chloride as catalyst. In this study, the transition and energy change for the each reaction step was calculated by the density functional theory program Dmol3 in Materials Studio 2017. and the results testified that there are two ring formation in the cycliztion process, and according to the result we proposed the mechanism of this cyclization reaction. We also use infrared and ultraviolet spectroscopy to monitor the reaction process in real time and prove the ring formation process. The reaction mechanism was firstly proposed at the basic results of above.
- Han, Siyu,Wang, Guosheng,Wang, Yuelan,Xu, Ronghui
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p. 308 - 313
(2021/07/19)
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- Merging C-H Vinylation with Switchable 6π-Electrocyclizations for Divergent Heterocycle Synthesis
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Pyridinium-containing polyheterocycles exhibit distinctive biological properties and interesting electrochemical and optical properties and thus are widely used as drugs, functional materials, and photocatalysts. Here, we describe a unified two-step strategy by merging Rh-catalyzed C-H vinylation with two switchable electrocyclizations, including aza-6π-electrocyclization and all-carbon-6π-electrocyclization, for rapid and divergent access to dihydropyridoisoquinoliniums and dihydrobenzoquinolines. Through computation, the high selectivity of aza-electrocyclization in the presence of an appropriate "HCl"source under either thermal conditions or photochemical conditions is shown to result from the favorable kinetics and symmetries of frontier orbitals. We further demonstrated the value of this protocol by the synthesis of several complex pyridinium-containing polyheterocycles, including the two alkaloids berberine and chelerythrine.
- Hu, Tianhui,Hua, Yuhui,Jiang, Xunjin,Qiu, Huijuan,Shen, Yang,Wu, Yifan,Xiong, Jing,Xu, Beibei,Zeng, Zhixiong,Zhang, Yandong
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supporting information
p. 15585 - 15594
(2020/10/20)
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- Method for fully synthesizing berberine
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The invention discloses a method for fully synthesizing berberine, and relates to a drug synthesis method. The method realizes the industrial full synthesis production of the berberine and is made from a bulk organic raw material catechol, the raw material is easily available, and the price is low; 2,3-dimethoxybenzaldehyde is obtained through selective formylation and methylation of the catechol;after a piperonyl ring is obtained through a catechol methylenenation reaction, piperonyl amine is synthesized through a one-step catalytic addition reaction, so that the synthesis steps of the piperonyl amine are shortened, the use of toxic cyanide is avoided, and the process is green and sustainable; condensation hydrogenation and salification reactions adopt a 'one-pot method', and thus the time and the energy are saved, and the cost is decreased. Industrialized full synthesis production of the berberine opens up large-scale production of the berberine, meets the clinical and research needs of the berberine in current anti-tumor, anti-blood pressure, anti-heart rhythm, blood sugar reduction, treatment of Alzheimer's disease and the like, provides effective drugs for reducing pain of patients, and has remarkable economic and social benefits.
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- Fibrauretine synthetic method (by machine translation)
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The invention relates to O-vanillin (11) as the starting material, by the acylation reaction generating 2 - acetoxy - 3 - methoxybenzaldehyde (12), by the bromo, hydrolysis reaction to produce the 2 - hydroxy - 6 - bromo - 3 - methoxybenzaldehyde (13), produced by the methylation reaction 6 - bromo - 2, 3 - dimethoxy benzaldehyde (14), produced by the condensation reaction of 2 - (6 - bromo - 2, 3 - dimethoxyphenyl) - 1, 3 - dioxolane (15); and then to 3, 4 - dimethoxy acetic acid (21) as raw materials, generated by the reduction reaction of the 3, 4 - dimethoxy ethanol (22), the acylation reaction generated by 3, 4 - dimethoxy new valeric acid environmentally (23), the acylation reaction is generated by the 2 - ethoxy - 3, 4 - dimethoxy new valeric acid environmentally (24), intermediate (15) and (24) after coupling, cyclized two-step reaction process for preparing the target product fibrauretin. (by machine translation)
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- A Unified Strategy for the Syntheses of the Isoquinolinium Alkaloids Berberine, Coptisine, and Jatrorrhizine
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Total syntheses of the antibacterial alkaloids berberine, coptisine, and jatrorrhizine have been achieved in four steps through a unified route. The key step of this strategy is an efficient intramolecular Friedel-Crafts alkoxyalkylation which, following oxidation, establishes the isoquinolinium core of these natural products. Herein, the design and development of this synthetic strategy, which has enabled the shortest and most efficient syntheses of these alkaloids reported to date, is described.
- Mori-Quiroz, Luis M.,Hedrick, Sidnee L.,De Los Santos, Andrew R.,Clift, Michael D.
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p. 4281 - 4284
(2018/07/29)
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- A room-temperature protocol to access isoquinolines through Ag(i) catalysed annulation of o-(1-alkynyl)arylaldehydes and ketones with NH4OAc: Elaboration to berberine and palmatine
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An efficient and mild protocol for the direct construction of aryl- and alkyl-substituted isoquinolines has been realized through silver nitrate catalyzed aromatic annulation of o-(1-alkynyl)arylaldehydes and ketones with ammonium acetate. The salient feature of this methodology is that this annulation could be effected at room temperature leading to a wide range of isoquinoline derivatives in good to excellent yields. Additionally, this approach has been employed to the synthesis of biologically important isoquinoline alkaloids such as berberine and palmatine.
- Reddy, Virsinha,Jadhav, Abhijeet S.,Vijaya Anand, Ramasamy
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p. 3732 - 3741
(2015/03/30)
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- Short and efficient syntheses of protoberberine alkaloids using palladium-catalyzed enolate arylation
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A concise synthesis of the biologically active alkaloid berberine is reported, and a versatile palladiumcatalyzed enolate arylation is used to form the isoquinoline core. The overall yield of 50%is a large improvement over the single, previous synthesis. By design, this modular route allows the rapid synthesis of other members of the protoberberine family (e.g., pseudocoptisine and palmatine) by substitution of the readily available aryl bromide and ketone coupling partners. Moreover, by combining enolate arylation with in situ functionalization, substituents can be rapidly and regioselectively introduced at the alkaloid C13 position, as demonstrated by the total synthesis of dehydrocorydaline. The avoidance of electrophilic aromatic substitution reactions to make the isoquinoline allows direct access to analogues possessing more varied electronic properties, such as the fluorine-containing derivative synthesized here.
- Gatland, Alice E.,Pilgrim, Ben S.,Procopiou, Panayiotis A.,Donohoe, Timothy J.
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supporting information
p. 14555 - 14558
(2015/02/19)
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- Pharmaceutical composition for the treatment of diabetes mellitus
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This invention relates to a pharmaceutical composition containing herbal ingredients for the treatment of diabetes mellitus and more particularly, to the antidiabetic composition comprising 1) 15 herbal ingredients (i.e., Shinseng Radix, Coptis Rhizoma, Ligustri Fructus Semen, Salix spp. Cortex, Rhei coreani Rhizoma, Anemarrhena Rhizoma, Salviae Radix, Scrophulariae Radix, Lycii Cortex Radicis, Reynoutriae Radix, Platycodi Radix, Astragali Radix, Puerariae Radix, Atractylis Rhizoma, and Morus alba Radix Cortex), 2) vitamins such as B1 and B6, and 3) zinc, manganese, chromium, germanium as inorganic materials. The antidiabetic herbal composition of this invention for the prevention and treatment of diabetes serves to lower the glucose level in diabetic patients and prevent the destruction of beta-cell in the pancreas, while increasing insulin secretion based on the mechanism of recovering the function of damaged beta-cell. Further, the antidiabetic herbal composition of this invention is quite effective in the treatment of insulin-dependent (type I) diabetes and non-insulin-dependent (type II) diabetes, since it shows the constant therapeutic effect due to better stability of therapeutic effect among individual patients.
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- Antifungal formulation comprising protoberberine derivatives and salts thereof
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The antifungal formulation comprising the novel compounds of the following chemical formulae (I) and (II) exhibit in vitro antifungal activity against fungi including cutaneous filamentous fungus, such as Epidermophyton, Microsporum, Trichophyton, Sporothrix schenckii, Aspergillus or Candida. The formulation of the present invention exhibit in vitro antifungal activity at the concentration of 1-100 mu g/ml. wherein R1, R2, and R4 may be the same or different, and represent C1-C5 alkoxy, R3 represents hydrogen or C1-C10 alkyl, A- represents inorganic acid ion, organic acid ion or halide, R5 represents hydrogen, pyridylmethyl, substituted pyridylmethyl or a group having the following chemical formula(XI) wherein Z1, Z2, Z3, Z4 and Z5 may be the same or different and represent hydrogen, halogen, C1-C5 alkyl, trifluoromethyl, phenyl, substituted phenyl, nitro, C1-C4 alkoxy, C1-C4 alkylamino, acetylamino, C1-C8 trialkyl ammonium, guanidinyl, methylthio, ethylthio, trifluoromethoxy, hydroxy, phenoxy, vinyl, carboxyl and C1-C2 alkoxycarbonyl group.
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- Pharmaceutically available protoberberine salts derivatives, and protoberberine salts derivatives, and protoberberine derivatives and salts thereof
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The novel compounds of the following chemical formulae (I) and (II) exhibit in vitro antifungal activity against fungi including cutaneous filamentous fungus, such as Epidermophyton, Microsporum, Trichophyton, Sporothrix schenckii, Aspergillus or Candida. The compounds of the present invention exhibit in vitro antifungal activity at the concentration of 1-100 μg/ml. STR1 wherein R1, R2, and R4 may be the same or different, and represent C1 -C5 alkoxy, R3 represents hydrogen or C1 -C10 alkyl, A- represents inorganic acid ion, organic acid ion or halide, R5 represents hydrogen, pyridylmethyl, substituted pyridylmethyl or a group having the following chemical formula(XI) STR2 wherein Z1, Z2, Z3, Z4 and Z5 may be the same or different and represent hydrogen, halogen, C1 -C5 alkyl, trifluoromethyl, phenyl, substituted phenyl, nitro, C1 -C4 alkoxy, C1 -C4 alkylamino, acetylamino, C1 -C8 trialkyl ammonium, guanidinyl, methylthio, ethylthio, trifluoromethoxy, hydroxy, phenoxy, vinyl, carboxyl and C1 -C2 alkoxycarbonyl group.
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- Reaction of Protoberberine-type Alkaloids. Part 12. A Facile Method for Regiospecific Oxygenation and Excited Oxidative Ring-cleavage of Berberine Alkaloids
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Regiospecific photo-oxygenation and photo-oxidative ring-cleavage of protoberberine alkaloids is described.Irradiation of a solution of dihydroberberine (1) in the presence of Rose Bengal under aerated conditions gave 13-oxidoberberine (3) along with berberine (2) in 80 and 7percent yields, respectively.In contrast, 7,8-dihydrocoralyne (5) gave 13-oxidocoralyne (7) in nearly quantitative yield when an aerated solution of (5) was heated in the dark.Irradiation of a solution of (3) containing Rose Bengal with visible light afforded 8,13a-epidioxy-9,10-dimethoxy-2,3-(methylenedioxy)- 13-oxo-5,6,13,13a-tetrahydro-8H-dibenzoquinolizine (11) in 90percent yield.Under the same conditions, however, (7) gave 2'-acetylpapaveraldine (14) in 88percent yield.On the other hand, when an alcoholic solution of (5) or (7) containing sodium alkoxide was irradiated with a mercury lamp (Vycol filter) under bubbling oxygen, 6,7-dimethoxyisoquinolone (16) and 3-alkoxy-5,6-dimethoxy-3-methylisobenzofuran-1(3H)-one (17) or (18) were obtained in moderate yields.A reaction mechanism which involves the initial formation of an epidioxy-intermediate was evidenced by the fact that the photolysis of (7) was carried out in the presence of borohydride anion to give (16) and 5,6-dimethoxy-3-methylisobenzofuran-1(3H)-one (19).Irradiation of (11) in the same fashion gave berberal (20) and 2-(2-formyl-3,4-dimethoxybenzoyl)-3,4-dihydro-6,7-(methylenedioxy)isoquinolin-1(2H)-one (21) in 72percent and 4percent yields, respectively.Possible mechanisms are also presented.Reduction of (3) with sodium borohydride gave (+/-)-ophiocarpine (9) and (+/-)-13-epiophiocarpine (10), with the ratio (9):(10) varying depending upon the nature of the alcohol used as solvent.An interpretation which rationalizes these observations is suggested.
- Kondo, Yoshikazu,Imai, Jiro,Inoue, Hideo
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p. 911 - 918
(2007/10/02)
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