- A new synthesis of alkyl (E)-(3-dimethylamino)acrylates
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A highly stereoselective one-step method for the synthesis of alkyl (E)-(3-dimethylamino)acrylates from N,N-dimethylformamide and ketene acetals is reported.
- Robertson, Jeffrey M.,Jones, Ian W.,Kayne, Kevin M.,Contreras, Cristina G.,Witter, Daniel J.,Bates, Robert B.,Hall Jr.
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Read Online
- Efficient synthesis of β-enaminoesters via highly stereoselective Reformatsky reaction with disubstituted formamides as novel electrophiles
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An efficient synthesis of various β-enaminoesters has been achieved via Reformatsky reaction with disubstituted formamides as novel electrophiles. The exclusive β-enaminoester E-isomers were obtained in 60-72% yield.
- Ke, Yi-Yin,Li, Yu-Jin,Jia, Jian-Hong,Sheng, Wei-Jian,Han, Liang,Gao, Jian-Rong
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Read Online
- Biaryl and atropisomeric biaryl aldehyde synthesis by one-step, metal-free benzannulation of aryl enals and propiolates
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A new method involving the benzannulation of aromatic enals and two alkyl propiolate molecules has been developed as a powerful route to biaryl aldehydes simply via the promotion of dimethyl amine. The benzannulation process in the absence of an oxidant additive tolerates successfully the formyl group in the enal component, leading to a straightforward one-step synthesis of biaryl and atropisomeric aldehydes. An enamine activation based on the aza-Michael addition of dimethyl amine to the propiolate and the amine elimination-based generation of cyclohexadiene intermediate constitute the major factors enabling the titled reactions. This journal is
- Hu, Deqing,Wan, Jie-Ping,Yang, Lu
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Read Online
- Silylamination of electrophilic alkynes
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The addition of simple silylamines to dialkyl acetylenecarboxylates was investigated yielding both E and Z-silylenamines in contrast to an earlier report. Silylamination was also achieved with propiolates, expanding the scope of the silylamination reactio
- Baines, Kim M.,McOnie, Sarah L.
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supporting information
(2021/12/23)
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- Preparation method of ethyl 3-(N,N-dimethylamino)acrylate
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The invention relates to a preparation method of ethyl 3-(N,N-dimethylamino)acrylate, which comprises the following steps: carrying out heating reaction on formic acid, ethyl acetate and dimethylamineto obtain ethyl 3-(N,N-dimethylamino)acrylate and water. The preparation method of the ethyl 3-(N,N-dimethylamino)acrylate is short in reaction route, high in yield and purity and low in safety risk.
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Paragraph 0027-0044
(2021/02/10)
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- Ethyl N,N-dimethylaminoacrylate synthesis method
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The invention relates to the technical field of synthesis of fine chemical intermediates, particularly to an ethyl N,N-dimethylaminoacrylate synthesis method, which comprises that ethyl acetate, carbon monoxide and dimethylamine are used as starting raw materials, and are subjected to a reaction under the action of a solid alkali catalyst to form the target product ethyl N,N-dimethylaminoacrylate,wherein the solid alkali catalyst is preferably a supported solid alkali catalyst. According to the present invention, the problems that the raw material source is difficult, the price is expensive,the process condition is harsh, the three-waste amount is high, the yield is low, the cost is high, the method is not suitable for industrial production and the like in the prior art are solved; and the synthesis method of the present invention has characteristics of convenient raw material source, low cost, environmentally-friendly reaction condition, substantially-reduced side-product, high total yield, high raw material utilization rate, low production cost and high product purity, and is suitable for large-scale industrial continuous production.
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Paragraph 0064-0075
(2019/04/26)
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- Synthesis method for N,N-dimethylaminoethyl acrylate
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The invention discloses a synthesis method for N,N-dimethylaminoethyl acrylate. The method includes the following steps that 1, raw material preparation is carried out, wherein ethyl acetate, carbon monoxide, dimethylamine carbonate and sodium ethoxide serve as raw material; 2, material blending is carried out, wherein the molar ratio of ethyl acetate to carbon monoxide to dimethylamine carbonate to sodium ethoxide is (3-4):(0.9-1.1):(1.0-1.30):(1.2-1.4); 3, ethyl acetate, dimethylamine carbonate and sodium ethoxide are added into a vessel, carbon monoxide is introduced into the vessel, the temperature in the kettle is controlled to be 45-50 DEG C at the pressure of 0.2-0.8 MPa, and a heat-preserved reaction is carried out for 10 h; 4, after the reaction is finished, reduced pressure distillation is carried out to distill off a solvent, and the distilled solvent is recycled; 5, water is added into the vessel, standing is carried out for layering, an oil phase enters a rectification system, and N,N-dimethylaminoethyl acrylate is obtained through rectification. The product synthesized with the method contains few impurities, the amount of wastewater is small, the water resource is saved, the yield is high and reaches 5%, and the content is increased to 99.5% or above from 98%.
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Paragraph 0018; 0019; 0020; 0021; 0022; 0023-0038
(2017/07/21)
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- Gold nanoparticles on OMS-2 for heterogeneously catalyzed aerobic oxidative α,β-dehydrogenation of β-heteroatom-substituted ketones
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In the presence of Au nanoparticles supported on manganese oxide OMS-2 (Au/OMS-2), various kinds of β-heteroatom-substituted α,β-unsaturated ketones (heteroatom = N, O, S) can be synthesized through α,β-dehydrogenation of the corresponding saturated ketones using O2 (in air) as the oxidant. The catalysis of Au/OMS-2 is truly heterogeneous, and the catalyst can be reused.
- Yoshii, Daichi,Jin, Xiongjie,Yatabe, Takafumi,Hasegawa, Jun-ya,Yamaguchi, Kazuya,Mizuno, Noritaka
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supporting information
p. 14314 - 14317
(2016/12/14)
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- 3-N,N-dimethylamino ethyl acrylate preparation method
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The invention relates to a 3-N,N-dimethylamino ethyl acrylate synthesis method, which comprises the following reaction process that under a medium pressure of 10-15 bar, piperidine is adopted as a catalyst, ethyl acetate reacts with sodium ethoxide and carbon monoxide to generate a formyl ethyl acetate sodium salt, and the formyl ethyl acetate sodium salt reacts with a dimethylamine hydrochloride to generate the 3-N,N-dimethylamino ethyl acrylate. According to the present invention, the piperidine is adopted as the catalyst, such that the 50 bar high pressure necessarily required in the prior art is reduced, and the complete reaction can be achieved within the medium-low pressure range of 10-15 bar so as to reduce the operation difficulty and the danger during the production.
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Paragraph 0010; 0021; 0022; 0026; 0027
(2016/10/08)
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- Alkoxide activation of aminoboranes towards selective amination
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Piece of the (inter)action: The interaction of alkoxides with the sp 2 Bpin (pin=pinacol) moiety in aminoboranes forms the in situ Lewis acid-base adduct [RO-→B(OR)2-N(R′)2] which enables the amino moiety to react as a strong nucleophile with several electrophiles, thus providing amino alcohols, β-enamino esters, and β-hydroxy amides in a direct and remarkably selective way (see scheme). Copyright
- Sole, Cristina,Fernandez, Elena
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supporting information
p. 11351 - 11355
(2013/11/06)
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- A facile approach to substituted acrylates by regioselective and stereoselective addition of thiols and amines to an alkynyl ester in water
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Water-promoted hydrothiolation and hydroamination of ethyl propiolate leading to highly regioselective and stereoselective formation of thioacrylates and β-enamino esters in excellent yields, by a simple, efficient, and environmentally friendly reaction p
- Randive, Nitin A.,Kumar, Varun,Nair, Vipin A.
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experimental part
p. 1329 - 1332
(2011/09/20)
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- Carbamoylcholine analogs as nicotinic acetylcholine receptor agonists-Structural modifications of 3-(dimethylamino)butyl dimethylcarbamate (DMABC)
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Compounds based on the 3-(dimethylamino)butyl dimethylcarbamate (DMABC) scaffold were synthesized and pharmacologically characterized at the α4β2, α3β4, α4β4 and α7 neuronal nicotinic acetylcholine receptors (nAChRs). The carbamate functionality and a small hydrophobic substituent in the C-3 position were found to be vital for the binding affinity to the nAChRs, whereas the carbamate nitrogen substituents were important for nAChR subtype selectivity. Finally, the compounds were found to be agonists at the α3β4 nAChR.
- Hansen, Camilla P.,Jensen, Anders A.,Balle, Thomas,Bitsch-Jensen, Klaus,Hassan, Mohamud M.,Liljefors, Tommy,Frolund, Bente
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supporting information; experimental part
p. 87 - 91
(2009/09/25)
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- Synthesis of (S,Z)-3-[(1H-indol-3-yl)methylidene]hexahydropyrrolo[1,2-a]pyrazin-4(1H)-one: an alternative, enaminone based, route to unsaturated cyclodipeptides
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A series of racemic and enantiopure (S,Z)-3-[(1H-indol-3-yl)methylidene]hexahydropyrrolo[1,2-a]pyrazin-4(1H)-one (cyclic Pro-ΔTrp) dipeptide analogues were prepared. Racemic analogues 6a-c were prepared by direct coupling of racemic cyclodipeptide enaminone (R,S)-5 with various indole derivatives. On the other hand, enantiopure analogues were prepared through a copper(I) catalyzed vinyl amidation reaction in which acyclic (S)-Pro-ΔTrp dipeptide analogues 20 and 21 were formed. Acyclic dipeptides were cyclized to enantiopure (S)-Pro-ΔTrp dipeptide analogues 24 and 25. For coupling reactions, vinyl bromides were prepared in several steps. From ethyl acetate (7), enaminone 8 was prepared and coupled with 2-methylindole and 2-phenylindole to give 9 and 10. Direct bromination of 3-(indole-3-yl)propenoates 9 and 10 at position 2 results in vinyl bromides 11 and 12. The Boc protecting group on the indole nitrogen 1′ in vinyl bromides 11 and 12 was introduced, before the copper(I) catalyzed coupling with N-Boc prolinamide 18 was performed. Enantiomeric purity of chiral intermediates and final products was determined mostly by HPLC or 1H NMR spectroscopy and X-ray diffraction.
- Wagger, Jernej,Gro?elj, Uro?,Meden, Anton,Svete, Jurij,Stanovnik, Branko
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p. 2801 - 2815
(2008/09/19)
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- Synthesis of unsaturated tryprostatin B analogues and determination of their enantiomeric purity with (S)-1-benzyl-6-methylpiperazine-2,5-dione
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Novel racemic and enantiomerically enriched unsaturated tryprostatin B analogues were synthesised by an enaminone-based strategy. The synthesis also features a novel coppers-catalysed dipeptide formation. In addition, the enantiomeric purity of an enantio
- Wagger, Jernej,Svete, Jurij,Stanovnik, Branko
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p. 1436 - 1442
(2008/12/21)
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- Alkynylation of N-tosylimines with aryl acetylenes promoted by ZnBr 2 and N,N-diisopropylethylamine in acetonitrile
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We found a suitable condition for the effective alkynylation of N-tosylimines with aryl acetylenes. The reaction of N-tosylimines and aryl acetylenes in the presence of ZnBr2 and DIEA (N,N- diisopropylethylamine) in CH3CN afforded the desired N-tosyl propargylamines in moderate to good yields.
- Lee, Ka Young,Lee, Chang Gon,Na, Jeong Eun,Kim, Jae Nyoung
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- Process for the preparation of β- aminoacrylic acid esters
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β-Aminoacrylic acid esters can be prepared by reacting acetic acid esters of the formula with aminal esters of the formula STR1 at 0.5-10 bar and 50°-170° C. in an aprotic polar solvent. The radicals R1 to R7 are as defined in the description.
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- Process for the preparation of μ-amino-acrylic acid esters
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β-Amino-acrylic acid esters of the formula can be obtained by reaction of β-hydroxy-acrylic acid ester alkali metal salts of the formula with ammonium salts of the formula according to the general reaction equation R1, R2, R3, R4, Me≈ and X? having the meaning indicated in the description and the reaction being carried out in an aprotic organic solvent, in which the reaction components are suspended, as the reaction medium and it being possible to replace a part of the aprotic organic solvent by a protic organic solvent which is miscible with the aprotic solvent to give a homogeneous phase.
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- Synthesis of 1-Aryl-5-(trifluoromethyl)-1H-pyrazole-4-carboxylic Acids and Esters
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Ethyl 1-aryl-5-(trifluoromethyl)-1H-pyrazole-4-carboxylates 2 were prepared by the condensation of arylhydrazines with ethyl 3-ethoxy-2-(trifluoroacetyl)-2-propenoate (1a) at low temperature.The corresponding acids were also synthesized.X-ray diffraction analysis of an amide derivative 4 verified the position of the trifluoromethyl group on the pyrazole ring.
- Beck, James R.,Wright, Fred L.
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p. 739 - 740
(2007/10/02)
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- REACTION OF GOLD'S REAGENT WITH ACTIVATED METHYLENE GROUPS DERIVED FROM ESTERS AND NITROARENES
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A series of esters and nitrotoluenes were reacted with Gold's reagent under basic conditions and were found to produce the corresponding dimethylamino methyleneated product in both cases.
- Gupton, John T.,Lizzi, Michael J.,Polk, Dale
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p. 939 - 946
(2007/10/02)
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- Macrocyclic Lactone Formation through Sulfide Contraction. Synthesis of (+/-)-Diplodialide A
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A methodology for the synthesis of macrocyclic β-keto-lactones from ω-hydroxy thioamides is described.The hydroxy thioamides were esterified with chloroacetyl chloride, and the resulting chloro esters underwent Eschenmoser sulfide contraction when treated with sodium iodide, diisopropylethylamine, and triethyl phosphite in acetonitrile.The β-keto lactones were obtained in 25-58 percent yield.The utility of the method was demonstrated by synthesis of diplodialide A.
- Ireland, Robert E.,Brown, Frank R.
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p. 1868 - 1880
(2007/10/02)
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- Orthoamides, XXXII. - Reactions of tert-Butoxy-N,N,N',N'-tetramethylmethanediamine with NH- and CH-acidic Compounds
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tert-Butoxy-N,N,N',N'-tetramethylmethanediamine (1) reacts with N-formylglycine ethyl ester (2) and with N-formyl-β-alanine ethyl ester (9) to form the aminomethylene compounds 3 and 10, respectively.Glycine ester is aminomethylenated by 1 at the acidic NH2 group to give the amidine 6.Dimethylaminoformaldehyde dimethyl acetal (5) is also suitable for this reaction.On reaction with 1 the compounds 3 as well as 6 yield the amidine 4.N-Monosubstituted formamides are transformed by 1 into formamidines 13.Reaction of isocyanoacetate 17 and 1 affords the enamine 18, whereas reaction of benzyl isonitrile with 1 gives the amidine 19. 2-Alkyl-Δ2-oxazolines 21, carboximidates 23, 25, and amidines 27 are aminomethylenated by 1 to yield the products 22, 24, 26, and 28, respectively.The vinylogous guanidinium salt 34 is obtained by reaction of 1 with N,N,N',N'-tetramethylacetamidinium tetrafluoroborate (31a).Phosphonates 36 react with 1 to afford the enamines 37.The reaction of 1 on ethyl trimethylsilylacetate (39) gives rise to formation of ethyl 3-dimethylaminoacrylate (11).
- Kantlehner, Willi,Wagner, Fritz,Bredereck, Hellmut
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p. 344 - 357
(2007/10/02)
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- β Aminocinnamonitriles as potential antiinflammatory agents
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A number of β aminocinnamonitriles have been prepared by the reaction of salts of acetonitrile and proprionitrile with benzonitrile. These materials were evaluated in the carrageenan antiinflammatory screen in Royal Hart, Wistar strain rats. Despite food weight gains with the parent molecule, β aminocinnamonitrile, only marginal activity was found in related compounds and some possible 'metabolites'.
- Lang Jr.,Cohen
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p. 441 - 443
(2007/10/08)
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