57196-75-5

The invention relates to a 2, 5 - diaryl five-membered heterocyclic aromatic preparation method, the method is to turn the diaryl Iodized salt compounds, five-membered heterocyclic aromatic compound, catalyst, ligand, alkali and solvent are mixed uniformly, in 100 °C -140 °C lower sealing reaction for 24 hours, the reaction solution obtained after the reaction is complete; the reaction solution are often gauge extraction, drying, concentration, column chromatography separation to obtain the 2, 5 - diaryl five-membered heterocyclic aromatic compounds. The invention belongs to a pot of reaction of the atom economy, simple operation, high yield, can realize the large-scale production, in functional organic material, biological active compounds and pharmaceutical synthesis of better industrial application prospect.

A novel porphyrin-based porous organic polymer PPOP-1(Pd) with bifunctional catalytic sites was constructed via imine condensation of tetra(4-aminophenyl)porphyrin and acenaphthenequinone. PPOP-1(Pd) containing Pd(ii)-porphyrin and Pd(ii)-α-diimine moieties exhibits excellent catalytic activity and outstanding reusability for tandem catalytic reactions of C-H arylation and Suzuki coupling.

The invention relates to a synthetic method for a diaryl furan compound with a formula (6) which is described in the specification. The synthetic method has a reaction route as shown in the specification. The synthetic method comprises the following steps: S1: allowing a compound with a formula (1) and a compound with a formula (2) to react in an organic solvent in the presence of a palladium catalyst, an organic ligand, an oxidant and an acidic compound, and after completion of the reaction, carrying out post-treatment so as to obtain a compound with a formula (3); S2, allowing the compound with the formula (3) to generate a self-cyclization reaction in an organic solvent in the presence of a catalyst, and after completion of the reaction, carrying out post-treatment so as to obtain a compound with a formula (4); and S3, allowing the compound with the formula (4) and a compound with a formula (5) to react in a solvent in the presence of a palladium catalyst, an organic ligand and an acidic compound at the atmosphere of oxygen, and after completion of the reaction, carrying out post-treatment so as to obtain a compound with a formula (6). The method provided by the invention realizes creative optimization in a plurality of technical characteristics through all steps, provides a novel synthetic method and a synthetic route for preparation of the compound, and has good industrialprospects and potential application values.

The invention relates to an epoxy-containing skeleton nitrile compound as shown in the following formula (4) and a synthesis method thereof. The synthesis method adopts the following reaction route: FORMULA, and comprises the following steps: S1: reacting a compound of a formula (1) with a compound of formula (2) in an organic solvent in the presence of a palladium catalyst, an organic ligand, anoxidizing agent and an acidic compound, performing post-treatment after finishing reaction to obtain a compound of formula (3); and S2: performing self-cyclization reaction on the compound of formula(3) in the organic solvent in the presence of the oxidizing agent, performing post-treatment after finishing reaction to obtain a compound of formula (4). The method creatively optimizes multiple technical features in each step so as to provide a novel synthesis method and synthesis route for preparation of such compounds and have excellent industrial prospects and potential application values.

The invention relates to a synthetic method of furan derivatives shown as a formula (6) as follows. The synthetic route of the method is shown in the specification. The method includes S1) allowing acompound shown as a formula (3) in an organic solvent to self-cyclize with the existence of an oxidant, and performing after-treatment when the reaction is finished to obtain a compound of a formula (4); and S2) reacting the compound of the formula (4) and a compound of a formula (5) in an oxygen atmosphere with the existence of a palladium catalyst, an organic ligand and an acidic compound in a solvent, and performing after-treatment after the reaction is finished to obtain a compound of the formula (6). A plurality of technical characteristics of each step are innovatively optimized in the method, and the brand-new synthetic method and synthetic route for preparing the compounds of this type are provided. The method has a good industrial prospect and good application value.

2,5-Diaryl-substituted furans were synthesized from the copper-catalyzed decarboxylative coupling of aryl-substituted aryl propiolic acids in the presence of H2O. The homocoupling of alkynyl carboxylic acids provided 1,4-diaryldiynes, which then reacted with H2O to give the desired furans through cyclization. Addition of the copper catalyst was critical, and the addition of a ligand increased the yield of products in both the homocoupling and cyclization reactions. In addition, thiophenes could be obtained when the reaction was conducted in the presence of Na2S.

An efficient gold-catalyzed domino reaction for the synthesis of furan derivatives from haloalkynes has been described. This transformation has provided a new route for the formation of C-O and C-C bonds that prepare functionalized furans.

A highly efficient synthesis of a wide range of 2,5-disubstituted furans from enyne acetates is described. The reactions are conducted by using Lewis acid and palladium catalyst and provide symmetrical and unsymmetrical products in good to excellent yields, with broad substrate scope, including a variety of aromatic and aliphatic substituents in the 2- and 5-position of the furan ring.

A general and practical synthetic method for aryl-substituted five-membered heterocycles has been developed. In the presence of KOH (30%), 1,4-diaryl-1,3-butadiynes undergo the cyclocondensation reaction with water, primary amines, and Na2S·9H2O in DMSO at 80 °C to afford 2,5-diarylfurans, 1,2,5-trisubstituted pyrroles, and 2,5-diarylthiophenes in good to high yields. Further studies have disclosed that aryl-substituted five-membered heterocycles can be also synthesized by a one-pot, two-step strategy from the terminal alkynes in DMSO firstly catalyzed by CuCl, and then via addition of KOH to promote the cyclocondensation of 1,3-butadiynes generated in situ.

2,5-Di(hetero)arylfurans are readily accessible in a pseudo five-component reaction via a Sonogashira-Glaser coupling sequence followed by a superbase-mediated (KOH/DMSO) cyclization in a consecutive one-pot fashion. Besides the straightforward synthesis of natural products and biologically active molecules all representatives are particularly interesting due to their bright blue luminescence with remarkably high quantum yields. The electronic structure of the title compounds is additionally studied with DFT computations.

Copper-impregnated magnetite is a versatile heterogeneous catalytic system for the synthesis of 1,3-diynes by the homocoupling of terminal alkynes. This catalyst does not require the use of pressurized oxygen as the oxidant and it does not need a solvent or harsh conditions to give the expected products. Moreover, the catalyst can be removed from the reaction medium simply by using a magnet. The reaction occurs at the lowest copper loading reported for any heterogeneous catalyst.

Palladium-catalyzed cross-coupling reactions of functionalized bromofurans with triarylbismuths have been described for the atom-economic synthesis of functionalized arylfuran systems. The coupling reactions using triarylbismuths with various 2-bromofurans and 2,5-dibromofuran underwent smoothly to afford the corresponding 2-arylfurans and 2,5-diarylfurans in high yields in a short reaction time (one hour). Georg Thieme Verlag Stuttgart · New York.

Woollins reagent was found to act as a highly chemoselective reagent for the reduction of a wide range of 1,4-enediones and 1,4-ynediones in methanol to afford the corresponding saturated 1,4-diketones in good yields under mild reaction conditions.

A regioselective synthesis of 2,5-disubstituted furans using copper(I) catalyst from haloalkynes in a one-pot procedure has been reported. This chemistry proceeds through the hydration reaction of 1,3-diynes, which can be readily prepared from the coupling reaction of haloalkynes in the presence of CuI. The procedure also can be used for the facile synthesis of 2,5-disubstituted thiophenes.

(Figure presented) A Au(I)-catalyzed hydroamination or hydration of 1,3-diynes to access 2,5-diamidopyrroles and 2,5-diamidofurans has been developed. This method can also be expanded to 2,5-disubstituted furans and 1,2,5-trisubstituted pyrroles including the formation of deuterated heterocycles and 18O-labeled furans.

The ionic liquid 1-butyl-3-methyl-imidazolium hydrogen sulfate, [bmim]HSO4, efficiently catalyzes Paal-Knorr furan synthesis without any organic solvent. A wide range of aliphatic and aromatic 1,4-diketones easily undergo condensations to form furan derivatives, providing a general and convenient procedure. The Paal-Knorr reaction of ester-substituted 1,4-diketones is first reported. The ionic liquid can be recovered and reused for subsequent runs without any appreciable loss of efficiency.

(Chemical Equation Presented) Step in time: 2,5-Disubstituted furans can be prepared from terminal alkynes in one pot using two successive catalytic reactions (see scheme; p-TSA=para-toluene-sulfonic acid). First, a 1,3-dienyl alkyl ether is produced by t

The Suzuki-Miyaura cross-coupling reaction of 2-(butyltellanyl) or 2,5-bis-(butyltellanyl)furans and thiophenes with potassium aryltrifluoroborate salts catalyzed by palladium afforded 2-aryl- or 2,5-diaryl-furans and thiophenes in moderate to good yields.

Several di- and triarylfuran derivatives were prepared in high yields from but-2-ene-1,4-diones/but-2-yne-1,4-diones using formic acid in the presence of a catalytic amount of palladium on carbon and in poly(ethylene glycol)-200 medium in a one-pot operation under microwave irradiation (1-5 min).

New experimental evidence for the mechanism of the Paal-Knorr reaction involving the acid-catalyzed cyclization of a 1,4-diketone to form a furan is reported.In aqueous or alcoholic solutions containing hydrochloric acid and in chloroform containing boron trifluoride-etherate d,l- and meso-3,4-diethyl-2,5-hexanediones (2r and 2m) cyclize at unequal rates; the stereochemical configuration of the unchanged dione is preserved during the reaction.This disagrees with commonly accepted mechanism involving the ring closure of the rapidly formed monoenol (11b) followed by loss of water.A pathway involving the rapid protonation of one of the carbonyls followed by the electrophilic attack on the protonated carbonyl by the enol being formed at the other carbonyl group (10c) is proposed to account for the difference in reaction rates between the diastereomers of 3,4-disubstituted 2,5-hexanediones (1-3).The following results also seem to support the intermediacy of 10c.The presence of two isopropyl groups in 3,4-diisopropyl-2,5-hexanedione (3) considerably reduces the rate of cyclization.The catalytic constants kH(+) for the cyclization of 2r and 2m are larger than the constants for enolization of methyl ketones.The diastereomers of 2,3-dimethyl- and 2,3-diethyl-1,4-diphenyl-1,4-butanediones (4 and 5), which could enolize only toward the center of the molecule, also react at different rates.The d,l and meso dideuterio analogs (d2-4r and d2-4m) exhibit a primary isotope effect during cyclization.The order of cyclization of 1,4-diphenyl-1,4-butanedione (6) and its analogs (7-9) reveals that the presence of electron-donating groups facilitate the reaction.

2,3-Dichloro-5,6-dicyanobenzoquinone (DDQ) reacts with primary and secondary aryl-substituted alcohols under mild conditions in dioxane solution to give the corresponding carbonyl compounds in high yields.In contrast to other oxidants, DDQ can be applied advantageously for the oxidation of hydroxyaryl-substituted alcohols.A mechanism involving participation of the phenolic hydroxyl group in the dehydrogenation reaction is discussed.Oxidations of hydroxyaryl-substituted alcohols by DDQ in methanolsolution resulting in the formation of benzoquinones by loss of the hydroxyaryl side chain are interpreted in terms of phenol oxidation.An example of a pyridine-catalyzed Smiles rearrangement of an o-hydroxy-substituted diphenyl ether is reported.