- Syntheses of 4-[(1H,3H)-pyrimidine-2,4-dion-1-yl]- and 4-[(1H,3H)-5- methylpyrimidine-2,4-dion-1-yl]-1,6-heptadienes
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Heptadienes containing nucleic bases are attractive building blocks for the synthesis of carbocyclic oligonucleotide analogs. Herein, we report an alternative synthetic route to 4-[(1H,3H)-pyrimidine-2,4-dion-1-yl]-1,6- heptadiene and 4-[(1H,3H)-5-methylpyrimidine-2,4-dion-1-yl]-1,6-heptadiene via building the pyrimidine ring utilizing 4-isocyanato-1,6-heptadiene intermediate.
- Bouhadir, Kamal H.,Zhou, Jing-Lan,Shevlin, Philip B.
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- Acetalization of alkenes catalyzed by Pd(OAc)2/NPMoV supported on activated carbon under a dioxygen atmosphere
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(Formula presented) The acetalization of terminal alkenes such as ethyl acrylate and acrylonitrile with alcohols under O2 was efficiently achieved by Pd(OAc)2 supported on activated carbon combined with molybdovanadophosphate (NPMoV). For example, ethyl acrylate was subjected to acetalization with EtOH acidified by CH3SO3H under O2 (1 atm) in the presence of [8 wt%Pd(OAc)2/C] and NPMoV to form ethyl 3,3-diethoxypropionate in quantitative yield.
- Kishi, Arata,Sakaguchi, Satoshi,Ishii, Yasutaka
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- C-Bridged Bispyrrolidines and Bispiperidines as New Ligands
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The preparation of methylene-bridged C2-symmetric nitrogen-heterocycles as a new class of ligands is described, including methylene-bridged pyridines, quinolones, piperidines and pyrrolidines. These methylene-bridged aromatic systems are obtained via a microwave assisted Ziegler-type reaction. The separation of diastereomers and the application of the copper complexes of these ligands for cyclopropanation reactions proves the applicability of these new types of ligands.
- Stumpf, Tim-Daniel J.,Steinbach, Manfred,H?ltke, Magdalene,Heuger, Gerold,Grasemann, Franka,Fr?hlich, Roland,Schindler, Siegfried,G?ttlich, Richard
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- One-pot production of diethyl maleate via catalytic conversion of raw lignocellulosic biomass
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The conversion of lignocellulose into a value-added chemical with high selectivity is of great significance but is a big challenge due to the structural diversities of biomass components. Here, we have reported an efficient approach for the one-step conversion of raw lignocellulose into diethyl maleate by the polyoxometalate ionic liquid [BSmim]CuPW12O40 in ethanol under mild conditions. The results reveal that all of the fractions in biomass, i.e., cellulose, lignin and hemicellulose, were simultaneously converted into diethyl maleate (DEM), achieving a 329.6 mg g-1 yield and 70.3% selectivity from corn stalk. Importantly, the performance of the ionic liquid catalyst [BSmim]CuPW12O40 was nearly twice that of CuHPW12O40, which can be attributed to the lower incorporation of the Cu2+ site in [BSmim]CuPW12O40. Hence, this process opens a promising route for producing bio-based bulk chemicals from raw lignocellulose without any pretreatment.
- Cai, Zhenping,Chen, Rujia,Zhang, Hao,Li, Fukun,Long, Jinxing,Jiang, Lilong,Li, Xuehui
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supporting information
p. 10116 - 10122
(2021/12/24)
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- Br?nsted Acid Catalyzed Tandem Defunctionalization of Biorenewable Ferulic acid and Derivates into Bio-Catechol
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An efficient conversion of biorenewable ferulic acid into bio-catechol has been developed. The transformation comprises two consecutive defunctionalizations of the substrate, that is, C?O (demethylation) and C?C (de-2-carboxyvinylation) bond cleavage, occurring in one step. The process only requires heating of ferulic acid with HCl (or H2SO4) as catalyst in pressurized hot water (250 °C, 50 bar N2). The versatility is shown on a variety of other (biorenewable) substrates yielding up to 84 % di- (catechol, resorcinol, hydroquinone) and trihydroxybenzenes (pyrogallol, hydroxyquinol), in most cases just requiring simple extraction as work-up.
- Bal, Mathias,Bomon, Jeroen,Liao, Yuhe,Maes, Bert U. W.,Sels, Bert F.,Sergeyev, Sergey,Van Den Broeck, Elias,Van Speybroeck, Veronique
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supporting information
p. 3063 - 3068
(2020/02/05)
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- Preparation method of ethyl 3-ethoxyacrylate
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The invention discloses a preparation method of ethyl 3-ethoxyacrylate. The preparation method comprises the following steps: (1) dropwise adding a certain amount of vinyl ethyl ether into trichloro-acetic chloride, controlling the temperature at 20 to 40 DEG C, and preserving heat for reacting for 1 to 10 hours; (2) evaporating low-boiling-point by-products under reduced pressure at the temperature of 40 DEG C; (3) adding organic alkali and ethanol, and preserving heat at 20 to 50 DEG C for reacting for 1 to 10 hours; (4) filtering, recovering a filter cake, and evaporating ethanol out of thefiltrate under reduced pressure at a temperature of 50 DEG C; (5) adding a certain amount of acid catalyst, heating to 50 to 100 DEG C, introducing nitrogen, and preserving heat for reacting for 1 to10 hours; (6) distilling under reduced pressure to obtain ethyl 3-ethoxyacrylate. The preparation method has the advantages of cheap and readily available raw materials, mild reaction conditions, easiness and convenience in operation, high yield, high product purity, few three wastes (waste gas, waste water and industrial residue), recovery of organic alkali from the generated solid waste, recyclability of the solvent and environmental friendliness, is a low-cost green synthesis technology, and is suitable for industrial production.
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Paragraph 0038-0049
(2019/03/30)
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- Preparation method of uracil
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The invention belongs to the technical field of organic synthesis, and concretely relates to a preparation method of uracil. The preparation method of uracil is characterized in that the uracil is obtained by condensing and cyclizing a compound represented by formula (I) with urea in the presence of an alkali; the formula (I) is shown in the description, and in the formula (I), R is a C1-3 alkyl group, and R1 is a methyl group or an ethyl group; and the compound of formula (I) is prepared from orthoformate and acetate under the action of the alkali. The method for synthesizing uracil from theorthoformate and acetate in a one-pot manner is reported for the first time; and the method has the advantages of cheap and easily available raw materials, simple process, convenience in operation, simplification of the post-treatment process due to the same alkali in the two steps, mild and easily controlled reaction product, no special devices, meeting of industrial mass production requirements,and good industrial application values.
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Paragraph 0041-0052
(2019/11/20)
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- Preparation method of 3,3-dialkoxylpropionate
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The invention belongs to the technical field of preparation of drug intermediates and in particular relates to a preparation method of 3,3-dialkoxylpropionate. The preparation method comprises the following steps: firstly, taking alkyl vinyl ether and trichloroacetyl chloride as raw materials; reacting under a certain condition to obtain an intermediate product 1,1,1-trichloro-4-alkoxyl-3-butene-2-one; reacting under an alkaline condition to obtain a target product 3,3-dialkoxylpropionate. The preparation method of the 3,3-dialkoxylpropionate, provided by the invention, has the following active effects that one raw material is directly used as a solvent (trichloroacetyl chloride) to react and the recycling and consumption of the solvent in a production process are reduced to a certain extent; after the reaction, an alcohol solvent can be recycled and is used for reacting for the next time, so that the recycling is realized and the scheme meets the requirements of green chemistry; a preparation process is simple, low in energy consumption and low in cost and can be in mass production.
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Paragraph 0025
(2017/09/02)
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- Method for preparing 2-formyl-3-ethyl oxopropionate
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The invention relates to a method for preparing 2-formyl-3-ethyl oxopropionate. The method comprises the steps of subsequently adding ethanol, potassium carbonate, ethyl formate and NaH into vinyl ethyl ether and trichloro-acetyl chloride, which serve as starting raw materials, and carrying out multistep reactions, thereby obtaining 2-formyl-3-ethyl oxopropionate. The obtained final product has the purity of 99.7% and the yield of 45%. The method is readily available in raw materials, mild in reaction conditions and low in cost and is applicable to large-scale production in factories.
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Paragraph 0007; 0021
(2017/09/01)
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- A method for synthesizing allah Geleg sandbank (by machine translation)
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The invention relates to a method for preparing anti-II type diabetes drug allah Geleg sandbank method for the synthesis of bulk drug (Anagliptin). The lack of commercial synthetic allah Geleg sandbank solve the technical problems of the method. Synthetic method comprises the following steps : (1) with vinyl ether and trichloro acetyl chloride as the raw material, passes through the three-step reaction to obtain the aldehyde protected intermediates 4 ; The 3-amino-5-methyl pyrazole condensation for dehydrating and gets pyrazolo pyrimidine mother nucleus; Carboxy b ester hydrolysis to obtain 2-methyl-pyrazolo [1,5-a] pyrimidin 6-carboxylic acid 6 ; (2) to L-proline as a raw material, passes through the methyl esterification, ammoniation, acetylation, Carbonitride reaction to obtain the chiral cyano pyrrolizinone intermediate 11 ; Chiral cyano pyrrolizinone intermediate 11 And diamine fragment 12 In alkaline conditions to obtain intermediate affinity substituted 13 ; Finally, intermediate 13 Under the conditions of the hydrochloric acid removal protection Boc base namely obtain cyanopentanoyl Azolylamine intermediate 14 ; (3) 2-methyl-pyrazolo [1,5-a] pyrimidine-6-carboxylic acid 6 The cyano Azolylamine intermediate 14 The condensation conditions to obtain the bulk drug allah Geleg sandbank coupled. (by machine translation)
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Paragraph 0011
(2016/10/10)
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- A kind of 3,4-dichloro-thiazole derivatives and process for their preparation and use
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The invention provides 3,4-dichloro isothiazole derivatives, their preparation method and application. The invention relates to a heterocyclic compound containing 3,4-dichloro isothiazol, and the compound is represented by the following chemical structural general formula. The invention discloses the structural general formula of the compound, a synthetic method of the compound and applications of the compound as pesticide, bactericide, anti-plant virus agent, and plant activator, and a technology of mixing the compound with agriculturally acceptable auxiliary agents or synergists for preparing pesticide, bactericide, anti-plant virus agent, and plant activator. The invention further discloses the combined application of the compound and the commercial pesticide, bactericide, anti-plant virus agent, and plant activator in controlling diseases, insect pests, and virus diseases in agriculture, forestry and gardening, and a preparation method of the compound and the commercial pesticide, bactericide, anti-plant virus agent, and plant activator.
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Paragraph 0038-0039; 0091-0092
(2016/10/08)
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- Platinum- and gold-catalyzed hydroalkoxylation and tetramerization of propiolate esters
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PtCl2 was found to efficiently catalyze intermolecular additions of propiolate esters with alcohols. The reaction of propiolate esters and alcohols in the presence of PtCl2 gave (E)-vinyl ethers as the major products at 60 °C, whereas alkyl 3,3-dialkoxypropanoates were predominantly obtained when the reaction temperature was set to 80°C. On the other hand, a novel regioselective tetramerization of propiolate esters catalyzed by AuCl3 under mild conditions afforded 1,2,5,6-tetrasubstituted- cyclooctatetraene (1,2,5,6-COT) in moderate yields.
- Chen, Qian,Zhang, Changyuan,Wen, Chunxiao,Fang, Jin,Du, Zhiyun,Wu, Dongling
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p. 101 - 105
(2014/08/18)
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- A novel and facile method for the synthesis of 2,3-disubstituted quinolines by a three-component coupling reaction
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A Lewis acid effectively catalyzed the three-component coupling reaction of an aromatic amine and aldehyde with ethyl propiolate, and the 2,3-disubstituted quinoline was regioselectively obtained in a good yield (up to 83% GC yield). Georg Thieme Verlag Stuttgart.
- Kikuchi, Satoshi,Iwai, Masahiro,Fukuzawa, Shin-Ichi
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p. 2639 - 2642
(2008/02/12)
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- INTEGRASE INHIBITORS 3
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The present invention provides a method of treatment or prophylaxis of a viral infection in a subject comprising administering to said subject an effective amount of a compound of formula (I) or a pharmaceutically acceptable derivative, salt or prodrug thereof. Compounds of formula (I) are also provided.
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Page/Page column 61
(2008/06/13)
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- Synthesis and RT inhibitory activity evaluation of new pyrimidine-based Seco-nucleosides
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Eleven new 3 ′,4 ′- seco acyclic nucleosides (4-14) were prepared by nucleophilic substitution of protected pyrimidine bases on ethyl 3,3-diethoxypropanoate (3). Structures were characterized spectroscopically and a brief analysis of their conformation in solution was performed by the vicinal coupling constants 3 J H 2′ aH 3′ and 3 J H 2′ bH 3′. In solid state, compound 6 forms a homodimer linked by hydrogen bonding. In preliminary tests all compounds show low toxicity and gentle activity against HIV-1 RT in vitro. Copyright Taylor & Francis Group, LLC.
- Vargas, Genaro,Escalona, Iker,Salas, Magali,Gordillo, Barbara,Sierra, Adolfo
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p. 243 - 257
(2007/10/03)
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- Pd(II)-catalyzed acetalization of terminal olefins with electron-withdrawing groups in supercritical carbon dioxide: selective control and mechanism
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Pd(II)-catalyzed acetalization of terminal olefins with electron-withdrawing groups was carried out smoothly in supercritical carbon dioxide under oxygen atmosphere when polystyrene-supported benzoquinone (PS-BQ) or CuII (CuI) chloride was employed as cocatalyst. The higher selectivity was achieved, without any chlorinated by-product detected, when using PS-BQ instead of CuII (or CuI) chloride. PS-BQ could be recycled with excellent catalytic activity remaining after each simple filtration. Chlorine ion was demonstrated to be a promoter. The different acetalization mechanisms were revealed by the subtle relationship of chlorine ion and benzoquinone (BQ) to the catalytic activity of PdCl2/PS-BQ, PdII-CuCl2 or Pd(OAc)2/PS-BQ.
- Wang, Zhao-Yang,Jiang, Huan-Feng,Ouyang, Xiao-Yue,Qi, Chao-Rong,Yang, Shao-Rong
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p. 9846 - 9854
(2007/10/03)
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- Ozonolysis of Olefins, I. - Ozonolysis of 1,4-Cyclohexadiene and Acid-Catalysed Reaction of Primary Cleavage Products
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The reaction of 1,4-cyclohexadiene (1) with ozone under different reaction conditions was investigated.Complete ozonolysis of 1 in chloroform led to a highly explosive ozonide.Oxidative ozonolysis gave malonic acid in 30percent yield, ozonolysis in alcoholic solutions of HCl gave alkyl 3,3-dialkoxypropionates 3 in 60-70percent yield and small amounts of the 1,1,3,3-tetraalkoxypropane 4 as well as dialkyl malonate 5.Partial ozonolysis of1 in HCl/methanol led to a mixture of 3,5 and the corresponding (Z)-3-hexene derivatives 6a-c.Depending on the reaction time and concentration of HCl, also the two methanol addition products 7b and 7d could be obtained.To verify the structure of these two compounds, 4-methoxycyclohexene (8) was ozonized in HCl/methanol, which gave a mixture of 7a-d.
- Mittelbach, Martin,Poklukar, Norbert,Junek, Hans
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p. 185 - 188
(2007/10/02)
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- Ozonolysis of Olefins, II; Linseed Oil as a Renewable Resource for Alkyl 3,3-Dialkoxypropanoates
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A new approach to the synthesis of alkyl 3,3-dialkoxypropanoates, which are important intermediates in organic synthesis, starting from fatty esters is described.Thus, ozonolysis of methyl linoleate and methyl linolenate in alcoholic hydrogen chloride affords a reaction mixture, from out of which the alkyl 3,3-dialkoxypropanoates can be isolated by fractional distillation in 60-65percent yield.Even linseed oil, which contains high amounts of linolic and linolenic acid, can be used as starting material, after conversion into the methyl esters by methanolysis.Byproducts of the ozonolysis can be oxidized to the corresponding carboxylic acids which are valuable intermediates in oleochemistry.
- Mittelbach, Martin,Poklukar, Norbert
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p. 331 - 332
(2007/10/02)
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- Highly Efficient Syntheses of Alkyl 3,3-Dialkoxypropanoates, Alkyl 4-Ethoxy-2-oxo-3-butenoates, and Monoprotected Malonaldehydes
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Haloform reaction of 4-alkoxy-1,1,1-trichloro-3-buten-2-ones, which can be obtained by acylation of enol ethers, gives 3,3-dialkoxypropanoic esters.Transacetalization of ethyl 3,3-diethoxypropanoate with 2,2-dimethyl-1,3-propanediol, followed by reduction and oxidation with DMSO/oxalyl chloride yields a monoprotected malonaldehyde. 4-Ethoxy-2-oxo-3-butenoates are synthesized either by acylation of enol ethers with alkoxalyl chlorides or by Claisen condensation of alkyl pyruvates with orthoesters.
- Tietze, Lutz-F.,Meier, Heinrich,Voss, Edgar
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p. 274 - 277
(2007/10/02)
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- CHEMISTRY OF ENOL ETHERS. LXXXVIII. CONDENSATION OF THE TETRAETHYLACETAL OF MALONALDEHYDE WITH β-SUBSTITUTED ENOL ALKYL ETHERS
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The action of β-substituted enol ethers on the tetraethylacetal of malonaldehyde gave the acetals of 1,5- and 1,7-dialdehydes.The nature of the substituent in the enol ether was found to affect the regioselectivity of the reaction: condensation with ethers containig an electron-wthdrawing substituent leads to 1,5-dialdehyde acetals, while condensation with ethers containig a strong electron donor substituent leads to 1,7-dialdehyde acetals.
- Makin, S. M.,Kruglikova, R. I.,Kharitonova, O. V.,Arshava, B. M.
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p. 1846 - 1849
(2007/10/02)
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- Thiazolidinylethylchlorocarbonates
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This invention relates to 2-(thiazolidin-2'-yl) ethylchlorocarbonates useful as intermediates in the synthesis of photographic image dye-providing materials and to their preparation by the reaction of the appropriate 2-(2'-hydroxyethyl)-thiazolidine with phosgene under certain conditions.
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- Preparation d'acetals fonctionnels
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Functional acetals can be prepared either by reaction of functional organomagnesium compounds with the mixed orthoformate C6H5O-CH()C2H5)2 or by reaction of carbonyl compounds with the acetylenic lithium compounds Li-CC-(CH2)n-CH(OC2H5)2 (n=0,1).
- Barbot, Francis,Miginiac, Philippe
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- Action d'organometalliques sur les dialkylphenylorthoformiates. Preparation facile d'acetals
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The reaction of dialkylphenylorthoformiates with organometallic compounds proceeds with a good yield, at room temperature, giving the corresponding dialkylacetals ; it allows an easy preparation of acetals which are otherwise difficult to prepare.
- Barbot, Francis,Poncini, Laurence,Randrianoelina, Benjamin,Miginiac, Philippe
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p. 4016 - 4035
(2007/10/02)
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- Action de l'hydroxyuree sur les esters α-acetyleniques
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Hydroxyurea, in its oxanion form NH2-CO-NHO(1-), reacts in basic medium by a 1,4-addition to α-acetylenic esters leading to the E and Z ethylenic β-ureidoxy esters isomers.The E isomer can be isolated and identified from reaction with ethyl tetrolate and ethyl propiolate.The Z isomer undergoes cyclisation in situ to give the 2-carboxamido-5-methyl-3-isoxazolone.With phenyl propiolate, the 3-hydroxy-5-phenyl isoxazole is directly obtained without isolation of the intermediate N-carboxamido derivative.In the case of ethyl propiolate two cyclic compounds are obtained: 3-hydroxyisoxazole and 2-N-carboxamido-5-ethoxy-3-isoxazolidinone.The formation of the former is due to the in situ cyclisation of the Z isomer.The isolation of the latter compound can be explained by solvent addition to the E β-ureidoxyacrylate intermadiate in a Michael addition followed by cyclisation.
- Lassalvy, Christiane,Petrus, Clement,Petrus, Francoise
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p. 175 - 180
(2007/10/02)
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- Synthesis of "Face to Face" Porphyrin Dimers Linked by 5,15-Substituents: Potential Binuclear Multielectron Redox Catalysts
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As part of the development of binuclear transition-metal complexes capable of facilitating multielectron redox reactions of small molecules (such as O2 and N2), we have devised an efficient and synthetically flexible route to 5,15-disubstituted porphyrins which affords multigram quantities of isomerically pure porphyrins without recourse to chromatography.The 5,15-substituents are principally amine ((CH2)nNHR (n = 1, 2, 3; R = H, CH3)) and acid chloride ((CH2)nC(O)Cl (n = 1, 2)) groups.Reactions of the two types of substituted porphyrins lead to a new class of "face to face" porphyrins with interporphyrin amide bridges of varying lenght (4-7 atoms).An amine-linked dimer has been produced by the reduction of an appropriate amide linkage.Purely hydrocarbon-linked dimers have also been prepared by the direct coupling of bis(dipyrrylmethanes) bridged by aliphatic (CH2)n (n = 4, 6) chains.The dimeric porphyrin compounds have been fully characterized by their visible and NMR spectra.The crystal and molecular structure of the bis(copper(II)) complex of one of the amide-linked dimers, the first such determination of a "face to face" porphyrin, is reported.Crystal data for Cu2C74N10O2H86*2H2O*C7H8: space group -P21/c; a = 11.878 (6) Angstroem, b = 13.304 (7) Angstroem; c = 23.725 (13) Angstroem, β = 114.60 (2) deg at -140 deg C; Z = 2.A crystallographic center of symmetry is imposed on the dimer.The structure was refined on all data including w on F2 of 0.103 and 0.152.For the portion of data having > 3?() (3213 observations) the values for R and Rw on F are 0.063 and 0.073.The spectral properties of these new porphyrin dimers are discussed with reference to the structural analysis.A striking feature of the structure is a shear-like displacement of one porphyrin unit with respect to the other by an average distance of 4.95 Angstroem.The Cu...Cu separation is 6.332 (4) Angstroem and the interpalanar separation of the two porphyrin rings is 3.87 Angstroem.In solution at ambient temperatures, conformational changes involving motions of the two porphyrin rings cause considerable line broadening in the 1H NMR spectra of all 5,15-bridged dimers.However, at temperatures above 90 deg C conformational equilibria are sufficiently rapid to produce well-resolved spectra.
- Collman, James P.,Chong, Anthony O.,Jameson, Geoffrey B.,Oakley, Richard T.,Rose, Eric,at al.
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p. 516 - 533
(2007/10/02)
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- ISOLATION, STRUCTURE AND SYNTHESIS OF 4-HYDROXYISOXAZOLE (TRIUMFEROL), A SEED GERMINATION INHIBITOR FROM AN AFRICAN PLANT
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The isolation, characterization and an efficient synthesis of 4-hydroxyisoxazole 1, a plant growth regulator isolated from an African plant is reported.It is a new compound, which despite the simple structure, had eluded synthesis.
- Kusumi, Takenori,Chang, Conway C.,Wheeler, Margaret,Kubo, Isao,Nakanishi, Koji,Naoki, Hideo
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p. 3451 - 3454
(2007/10/02)
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