- Ozonolysis of α-angelica lactone: a renewable route to malonates
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Industrially relevant intermediates such as malonic acid, malonates and 3-oxopropionates can be easily accessed by ozonolysis of α-angelica lactone, derived from the platform chemical levulinic acid. The roles of the solvent and of the quenching conditions are of key importance for the outcome of the reaction.
- Dell’Acqua, Andrea,Stadler, Bernhard M.,Tin, Sergey,Wille, Lukas,de Vries, Johannes G.
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supporting information
p. 10524 - 10527
(2021/10/19)
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- Green preparation method of uracil
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The invention relates to a green preparation method of uracil, which comprises the following steps: proportionally mixing acetate, alkali and a benzene solvent in a reaction bottle to obtain a mixed solution, introducing carbon monoxide, pressurizing to generate aldehyde, adding a hydrogen chloride alcohol solution into the reaction bottle, and carrying out condensation reaction on aldehyde and the hydrogen chloride alcohol solution to obtain acetal, and adding urea into the reaction bottle, reacting acetal with urea to obtain a condensate, adding alkali into the reaction bottle, reacting alkali with the condensate to generate uracil sodium salt, adding acidic water into the reaction bottle, crystallizing, cooling, and filtering to obtain uracil. Carbon monoxide and acetate are innovatively used as raw materials, alkali such as sodium methoxide is used for one-pot catalytic synthesis of uracil, the synthesis method in the whole process is mild in condition, simple in process and high in yield and purity, the purposes of few three wastes and environmental protection are achieved, and the method has a good large-scale application prospect.
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Paragraph 0025
(2021/01/25)
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- Preparation method of methyl 3-methoxyacrylate
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The invention relates to a synthetic method of methyl 3-methoxyacrylate. The method is characterized by comprising the following steps that: (1) methyl 3, 3-dimethoxypropionate is synthesized from ketene dimer and trimethyl orthoformate at 25-90 DEG C under the catalytic action of an alkaline substance by taking alcohols as a solvent, and the molar ratio of the ketene dimer to trimethyl orthoformate to the alkaline substance is controlled to be 1: (1.0-5.0): (0.5-5.0); and (2) after the reaction is finished, the methyl 3, 3-dimethoxypropionate is cracked under the action of a catalyst to generate 3-methoxy methyl acrylate, and controlling the molar ratio of the methyl 3, 3-dimethoxypropionate to the catalyst to be 1: (1.0-5.0) and the reaction temperature to be 100-200 DEG C. According tothe method, raw materials are cheap and easy to obtain; the synthesis method is simple to operate; the reaction conditions are mild; requirements on equipment are low; and requirements of industrial large-scale production are met.
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Paragraph 0020-0026
(2020/12/10)
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- Preparation process of MAME (methyl 3-methoxyacrylate)
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The invention provides a preparation process of MAME (methyl 3-methoxyacrylate) and belongs to the technical field of synthesis of organic compounds. According to the preparation process, methyl acrylate and excess methanol taken as starting raw materials are subjected to an addition-etherification reaction in an oxygen atmosphere under the action of a synthetic catalyst, a product is subjected tofiltration and extraction, methyl 3,3-dimethoxypropionate is obtained and subjected to a catalytic cracking reaction, MAME and methanol are generated, the target product MAME is obtained through distillation, and methanol is recovered, wherein the synthetic catalyst is cobalt oxide, indium oxide or a mixture of cobalt oxide and indium oxide in any proportion. The preparation process is simple andefficient, the yield of the product MAME is higher and reaches 78%-82.4%, the catalyst can be recycled for a long time, corrosive and toxic substances are avoided, reaction equipment cannot be corroded, industrial production can be realized, and considerable economic benefits are created.
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Paragraph 0016-0020
(2018/04/26)
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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 0029; 0033; 0037
(2017/09/02)
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- Synthesizing method for 3-methoxyacrylate
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The present invention relates to a synthesizing method for 3-methoxy-3-ethoxy methyl propionate, and belongs to the field of chemistry. The synthesizing step comprises the following steps: introducing methyl vinyl ether into trichloroacetyl chloride, and insulating until a reaction is completed; combining BJ01 with anhydrous methanol, adding an acid-binding agent I, and insulating until a reaction is completed; and mixing BJ02 with an organic solvent 2, adding a catalyst, and insulating until a reaction is completed to obtain the 3-methoxyacrylate. The synthesizing method for the 3-methoxyacrylate has the advantages of few reaction steps, easiness in operation, less waste gas, waste water and waste residues, high yield, high purity of products, and inexpensive and easily available raw materials. All the steps have no harsh conditions and are simple in operation and environmentally-friendly, and the solvent are easily recycled and reused, so that the synthesizing method is suitable for industrial production.
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Paragraph 0019; 0025
(2016/10/17)
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- Atom-economical synthesis of 3,3,3-trifluoropropanal dialkyl acetals through Pd/C catalyzed acetalization of 3,3,3-trifluoropropene
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A facile and efficient procedure for one-step synthesis of 3,3,3-trifluoropropanal dialkyl acetals from readily available 3,3,3-trifluoropropene (TFP) has been developed. The catalyst can be recycled for 4 times without obvious deactivation. This process provides a novel and atom-economical synthetic strategy for the preparation of functional CF3-containing compounds.
- Kang, Jian-Ping,Lu, Ju-You,Li, Yang,Wang, Zhi-Xuan,Mao, Wei,Lu, Jian
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p. 39387 - 39391
(2016/06/01)
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- Acid-catalyzed oxidation of levulinate derivatives to succinates under mild conditions
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Levulinate derivatives are an attractive platform for the production of renewable chemicals. Here we report on the oxidation of methyl levulinate into dimethyl succinate with peroxides under mild conditions using Br?nsted and Lewis acid catalysts. Selectivities to succinate and acetate derivatives of approximately 60 and 40 %, respectively, were obtained with strong Br?nsted acids in methanol. Although the molecular structure (i.e., carbon-chain length and branching around the C=O group) and the oxidant type affect the product distribution, solvent choice has the strongest impact on changing the location of oxygen insertion into the carbon backbone. Specifically, switching the solvent from methanol to heptane resulted in a decrease in the succinate/acetate ratio from 1.6 to 0.3. In contrast to Br?nsted acids, we demonstrate that the nature of the metal cation is responsible for changing the reaction selectivity of water-tolerant Lewis acidic triflate salts.
- Wang, Yuran,Vogelgsang, Ferdinand,Román-Leshkov, Yuriy
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p. 916 - 920
(2015/03/18)
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- Catalytic oxidative decarboxylation of malic acid into dimethyl malonate in methanol with dioxygen
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If you've got it, use it: Malic acid is converted into dimethyl malonate by a direct, one-pot process. The process is cyanide- and halide-free. Phosphovanadomolybdates serve as bifunctional catalysts, effecting the oxidative decarboxylation and esterification in a consecutive manner. Oxidative C-C bond cleavage first forms hemiacetals. The results serve as example for the production of valuable chemicals by fully utilizing the oxygen atoms and basic structure inherent to biomass products.
- Liu, Junxia,Du, Zhongtian,Yang, Yanliang,Lu, Tianliang,Lu, Fang,Xu, Jie
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p. 2151 - 2154
(2013/01/15)
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- Research and development of the catalytic oxidation of methylacrylate to 3,3-dimethoxy methyl propionate
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A selective synthesis of 3,3-dimethoxy methyl propionate has been developed using a green approach, in which the key step is a palladium-catalyzed oxidation of methylacrylate in methanol using oxygen as oxidant. The relationship between several reaction p
- Tanaka, Yoshiyuki,Takahara, Jun P.,Lempers, Hans E.B.
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experimental part
p. 548 - 554
(2010/04/22)
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- PROCESS FOR THE PREPARATION OF ALKYL 3,3-DIALKOXYPROPIONATES
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The present invention relates to a continuous process for preparing alkyl 3,3-dialkoxy-propionates of the formula (RO)2CHCH2CO2R, wherein R is C1-6 alkyl, by reacting ketene with an ortho formate of formula (RO)3CH in the presence of an acidic catalyst, characterized in that the reaction is carried out in a loop reactor.
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Page/Page column 7-8
(2009/06/27)
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- Palladium-catalyzed aerobic oxidation of terminal olefins with electron-withdrawing groups in scCO2
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Product control of palladium-catalyzed aerobic oxidation of terminal olefins with electron-withdrawing groups can be achieved through modifying reaction conditions. When the oxidant, such as CuCl2/O2, benzoquinone/O2 or O2, was present in scCO2, aerobic oxidation of terminal olefins goes smoothly. With enough MeOH and sufficient oxygen, acetalization preponderated over cyclotrimerization, while with little MeOH as co-solvent in scCO2 or no MeOH in DMF and an appropriate pressure of O2, cyclotrimerization of terminal olefins became the dominated reaction. When oxygen is absent and triethylamine was added into the reaction system, palladium-catalyzed C-N bond formation occurs to produce β-amino acid derivatives as the sole product.
- Jiang, Huan-Feng,Shen, Yan-Xia,Wang, Zhao-Yang
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p. 508 - 514
(2008/03/28)
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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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- Cyclopropyl building blocks for organic synthesis, part 100.[?] Advanced syntheses of cyclopropylideneacetates - Versatile multifunctional building blocks for organic synthesis
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A well reproducible and inexpensive preparation of the cyclopropylideneacetates 2-4 has been developed. The key intermediate 2-(1′-mesyloxycyclopropyl)acetic acid (8), produced either from methyl phenylacetate (1) or 3,3-dimethoxypropionate (5-Me) and 3,3-diethoxypropionate (5-Et) in a sequence of Kulinkovich reductive cyclopropanation, mesylation and oxidative cleavage or cleavage and oxidation, respectively, was either converted to the benzyl ester 11b, or chlorinated (brominated) via the in situ formed acid chloride. The α-chloro- 12a and α-bromo ester 12b were dehydromesylated by treatment with triethylamine to furnish methyl 2-chloro-2-cyclopropylideneacetate (3-Me) and the 2-bromo analogue 4-Me with an overall yield of 68% (65%, 68%) and 52% (49%, 51%) respectively, starting from 1 (5-Me, 5-Et). The parent benzyl cyclopropylideneacetate 2-Bn was obtained by dehydromesylation of 11b with potassium t-butoxide in t-butyl methyl ether with an overall yield of 60% (57%, 9%) from 1 (5-Me, 5-Et).
- Limbach, Michael,Dalai, Suryakanta,De Meijere, Armin
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p. 760 - 766
(2007/10/03)
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- Process research on the synthesis of silthiofam: A novel fungicide for wheat
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The development of an efficient, low-cost synthesis of the novel wheat fungicide silthiofam (1) is described. Improvements to the original Discovery route allowed 300 kg of material to be prepared in two, overlapping pilot-plant campaigns. Thereafter, efforts were focused on further optimizing the pilot-plant route, and on devising alternate, lower cost routes to silthiofam. One potential new route involved a cydoaddition reaction between 3-mereapto-2-butanone and N-(2-propenyl)-3-trimethylsilyl-propynamide. The cyclic product could be directly dehydrated to silthiofam, however the overall yield was modest, raw material costs were high, and there were purification problems. The route ultimately selected for development proceeds in 6 chemical steps and about 60% yield from the inexpensive precursors 3-chloro-2-butanone and methyl 3-methoxyacrylate. Key features of the route are a novel thiophene-3-carboxylate synthesis involving cycloaddition of 3-mercapto-2-butanone with the acrylate followed by acid catalyzed aromatization, the room temperature formation and silylation of a thiophene-3-carboxylate dianion, and conversion of the resulting carboxylic acid into silthiofam with negligible loss of the silyl group. The process involves isolation of just two intermediates, only one of which is purified, and uses only three organic solvents, all of which are recycled. It can be run safely on large scale to give highpurity silthiofam.
- Phillips, Gary,Fevig, Thomas L.,Lau, Patrick H.,Klemm, George H.,Mao, Michael K.,Ma, Chun,Gloeckner, James A.,Clark, Art S.
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p. 357 - 366
(2013/09/06)
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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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p. 523 - 525
(2007/10/03)
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- Palladium(II)-catalyzed oxidation of acrylate esters to acetals in supercritical carbon dioxide
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The development of a new palladium(II)-catalyzed oxidation of methyl acrylate, affording methyl 3,3-dimethoxypropanoate in excellent conversion and selectivity in supercritical CO2, is presented.
- Jia, Lanqi,Jiang, Huanfeng,Li, Jinheng
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p. 985 - 986
(2007/10/03)
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- Stereoselective addition of alcohol to acetylenecarboxylate catalyzed by silver(I) salt
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A silver(I) salt catalyzed the stereoselective trans addition of alcohol to dimethyl acetylenedicarboxylate smoothly under mild conditions to afford dimethyl methoxyfumarate in a quantitative yield.
- Kataoka, Yasutaka,Matsumoto, Osamu,Tani, Kazuhide
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p. 727 - 728
(2007/10/03)
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- Claisen Orthoester Rearrangement in the Direct Preparation of Z-Isositsirikine and Z-Geissoschizine Derivatives Possessing the Right Oxidation State at C-17
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The Claisen orthoester rearrangement utilizing allylic alcohol 1 (or 2) and trimethyl 3-methoxyorthopropionate 13a leads to Z-isositsirikine derivatives 21a-22a (or 23a-24a) possessing one RO-function at C-17.In the cases of trialkyl 3,3-dialkoxyorthopropionates , the intermediate ketene acetals 25a,b do not rearrange according to the Claisen mechanism to form compounds 26a,b and/or possessing two two RO-functions at C-17.Syntheses of the intermediate orthoesters, trimethyl 3-methoxyorthopropionate 13a, trimethyl 3,3-dimethoxyorthopropionate 14a, trimethyl trans-3-methoxyorthoacrylate 20c, and triethyl 3,3-diethoxyorthopropionate 14b are described.
- Lounasmaa, Mauri,Hanhinen, Pirjo,Jokela, Reija
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p. 8623 - 8648
(2007/10/02)
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- Palladium(II)-catalyzed acetalization of allylic acetates and its utilization for the synthesis of 2-cyanovinyl ketones
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α-Cyanoallyl acetate (1 a), when treated with methanol in the presence of bis(acetonitrile)dichloropalladium(II) catalyst, is acetalized at the terminal olefinic carbon to give 1-cyano-3,3-dimethoxypropyl acetate (2). γ-Substituted α-cyanoallyl acetates give 3-substituted 1-cyano-3-oxo-propyl acetates 5 from which 2-cyanovinyl ketones 11 are obtained in good yields.
- Hosokawa,Aoki,Murahashi
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p. 558 - 561
(2007/10/02)
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- Ozonolyse von Olefinen, III: Saeurekatalysierte Ozonolyse von 3-Hexen-1,6- und 2-Penten-1,5-dicarbonylderivaten
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The ozonolysis of mono-unsaturated compounds containing the structural element =CH-CH2-R was investigated.Reductive ozonolysis of (E)-3-hexene-1,6-dioic acid gives methyl 3,3-dimethoxypropanoate (2), whereas ozonolysis of dimethyl (E)-3-hexene-1,6-dioate (1a) and (Z)-1,1,6,6-tetramethoxy-3-hexene (1b) in a methanolic solution of HCl leads to a mixture of 2, dimethyl malonate (3a) and 1,1,3,3-tetramethoxypropane (3b).The homologuos derivatives, dimethyl glutaconate (4a) and 1,1,5,5-tetramethoxy-2-pentene (4b), were ozonized to give mixtures of 2, 3, dimethyl oxalate (5), methyl 2,2-dimethoxyacetate (6a), and 1,1,2,2-tetramethoxyethane (6b).The ratios of the various reaction products were determined by gas chromatography.In each case the formation of the bifunctional derivatives 2 and 6a was favoured.
- Poklukar, Norbert,Mittelbach, Martin
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p. 203 - 207
(2007/10/02)
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- NUCLEOPHILIC ADDITIONS TO α,β-UNSATURATED SULPHONES. IV. ADDITION-DESULPHONYLATION IN THE REACTIONS OF VINYL SULPHONES BEARING A β CARBONYL FUNCTION
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Reactions of oxygen, nitrogen and carbon nucleophiles with β-methoxycarbonylvinyl phenyl sulphone, 1, β-acetylvinyl phenyl sulphone, 2, and 3-phenylsulphonylcyclopentenone, 3, have been investigated.The addition of methanol and pyrrolidine to the sulphone 1 is followed by elimination of benzenesulphinate, in analogy with earlier observations on β-substituted α,β-unsaturated sulphones.Elimination of sulphinate is also observed, for the first time, in the reaction of 1 and 2 with cycloalkanone enamines.The cyclic keto sulphone 3, on the contrary, reacts with a cyclopentanone enamine to give a cyclobutane adduct in which the sulphone group is retained.
- Benedetti, Fabio,Fabrissin, Silvio,Fagotto, Roberto,Risaliti, Amerigo
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p. 613 - 618
(2007/10/02)
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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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