626-35-7Relevant articles and documents
Efficient Synthesis of α-Ketothioamides From α-Nitroketones, Amines or DMF and Elemental Sulfur Under Oxidant-Free Conditions
Zhang, Zhenlei,Yang, Jiusi,Yu, Renjie,Wu, Kairui,Bu, Jiping,Li, Shaoke,Qian, Peng,Sheng, Liangquan
supporting information, p. 5209 - 5212 (2021/10/19)
We have developed a practical, general protocol for denitration of readily available α-nitroketones with sulfur and amines to access a broad range of α-ketothioamides under mild conditions. Such a reaction proceeds under metal-, oxidant-, and catalyst-free conditions to provide synthetically useful α-ketothioamides. Furthermore, the mild reaction conditions tolerate a wide range of substrates especially for the synthesis of aliphatic α-ketothioamides which are rarely reported.
Transesterification of Methyl 2-Nitroacetate to Superior Esters
Corsi, Massimo,Machetti, Fabrizio,Magnolfi, Stefano
, (2020/03/19)
Methyl 2-nitroacetate and methyl acetoacetate have in common the presence of an electron-withdrawing substituent geminal to the methyl ester function but the well-known ease of thermal transesterification of methyl acetoacetate has not been found in methyl 2-nitroacetate. The latter gives uncatalysed thermal transesterification only in low yield and at a temperature higher than that of methyl acetoacetate. Comparative experiments provided further insight into the reactions; protic and Lewis acid catalysts promoted the smooth exchange of the alkanoyl groups, observing first the transesterification of methyl 2-nitroacetate with ethanol, already proved difficult to proceed. Dibutyltin(IV)oxide (DBTO) catalyst offered the spur to set up a convenient synthetic methodology from methyl 2-nitroacetate, encompassing higher molecular weight and functionalised alcohols: aliphatic, unsaturated and oxidation sensitive species were suited to react, delivering the corresponding 2-nitroacetate esters in good yields in most cases.
Nitro-acetic acid ethyl ester and intermediate preparation method (by machine translation)
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Paragraph 0047; 0048, (2017/11/16)
The invention discloses a nitro-acetic acid ethyl ester and intermediate preparation method. 2 - nitro-acetyl-acetic acid ethyl ester preparation method, comprises the following steps: the acetyl ethyl acetate and through activating the nitric acid reagent from different pipeline entering the micro-channel reactor, the reaction is carried out; wherein the reaction temperature is 5 - 50 °C. By using micro-channel reactor preparing nitro-acetic acid ethyl ester, not only can greatly shorten the reaction time, to enhance the efficiency of the reaction, but also can reduce the generation of by-products, the security is increased, the production cost is reduced, can be suitable for industrial production. (by machine translation)
Catalytic Enantioselective Desymmetrization of Norbornenoquinones via C(sp2)-H Alkylation
Sarkar, Rahul,Mukherjee, Santanu
supporting information, p. 6160 - 6163 (2016/12/09)
The enantioselective Diels-Alder (DA) reaction with monosubstituted p-benzoquinones is an unmet challenge. A new approach for the enantioselective synthesis of monosubstituted quinone-DA adducts is presented based on C(sp2)-H alkylative desymmetrization of meso-DA adducts. Catalyzed by a tertiary amino-thiourea derivative, this reaction utilizes nitroalkanes as the alkylating agents and generates densely functionalized products bearing at least four contiguous stereogenic centers remote from the reaction site with excellent enantioselectivities.
Synthesis of α-Nitro Carbonyls via Nitrations in Flow
Chentsova, Anna,Ushakov, Dmitry B.,Seeberger, Peter H.,Gilmore, Kerry
, p. 9415 - 9421 (2016/10/17)
Reported is a safe, rapid method for the synthesis of α-nitro esters via the trapping of nitronium ions. The two-stage nitration and subsequent deacetylation of readily available 1,3-dicarbonyl compounds was achieved using a biphasic semicontinuous approach. α-Nitro esters and amides were obtained in good overall yields (53-84%). Some of the α-nitro-1,3-dicarbonyl intermediates exhibit enhanced reactivity and undergo an acid-catalyzed Nef-type reaction to α-oxo-carbonyls.
Nucleophilic substitution accompanying carbon-carbon bond cleavage assisted by a nitro group
Nakaike, Yumi,Taba, Noriko,Itoh, Shinobu,Tobe, Yoshito,Nishiwaki, Nagatoshi,Ariga, Masahiro
experimental part, p. 2413 - 2417 (2009/09/08)
A 2-nitrated 3-oxoester reacted with amines or alcohols to afford unsymmetrical malonic acid derivatives as a result of nucleophilic substitution accompanying C-C bond cleavage. The 2-nitrated 3-oxoester easily formed ammonium salts with amines. When the amine is liberated from the salt under equilibrium, nucleophilic amine and electrophilic keto ester locate close to each other. This intimate pair effect causes a pseudo intramolecular reaction to occur, giving rise to effective substitution under mild conditions.
Transforming natural amino acids into α-alkyl-substituted amino acids with the help of the HOF·CH3CN complex
Harel, Tal,Rozen, Shlomo
, p. 6500 - 6503 (2008/02/10)
(Chemical Equation Presented) α-Alkyl amino acids can be efficiently prepared in high yields from the respective amino acids themselves. The key step is the oxidation of the amine function to create the corresponding α-nitro acid in a fast and very high yield reaction followed by phase-transfer alkylation and finally reduction to the desired α-alkyl amino acid. Several such acids containing aromatic rings or additional carboxylic groups and acids with steric hindrance at the α-position are suitable substrates. Several alkyl halides were examined as alkylating agents.
Oxidation of azides by the HOF·CH3CN: A novel synthesis of nitro compounds
Carmeli, Mira,Rozen, Shlomo
, p. 4585 - 4589 (2007/10/03)
The HOF·CH3CN complex, readily prepared by passing F 2 through aqueous acetonitrile, is an exceptionally efficient oxygen transfer agent. It is unique in its capacity to oxidize various azides into the corresponding nitro derivatives. This method requires short reactions times and room temperature or below, and the desired nitro compounds were usually isolated in very good yields. The respective nitroso derivatives are believed to be the intermediates in this reaction. Functional groups such as aromatic rings, ketones, nitriles, halides, alcohols, and esters are tolerated. Sulfides react with HOF·CH3CN usually at the same rate as azides. Amines and olefins, however, react faster, so they have to be protected first. Nitro derivatives with various oxygen isotopes can be made using the labeled H 18OF·CH3CN. In the case of chiral azides the stereochemistry around the nitrogen-bonded carbons is retained.
Domino processes as a tool for recovering substandard reactions. Synthesis and use of nitroacetic acid esters and amides
Scardovi, Noemi,Casalini, Andrea,Peri, Francesca,Righi, Paolo
, p. 965 - 968 (2007/10/03)
(equation presented) Elusive nitroacetic acid esters and amides were obtained through a halogen exchange reaction of the corresponding bromoacetic acid derivatives with polymer-supported nitrite anion. The process is flawed by a side product catalyzed deg
An efficient procedure for the esterification of nitroacetic acid :Application to the preparation of Merrifield resin-bound nitroacetate
Sylvain, Catherine,Wagner, Alain,Mioskowski, Charles
, p. 875 - 878 (2007/10/03)
Nitroacetic esters are prepared in good yield by reaction, at 0 °C, of nitroacetic acid with various alcohols in the presence of DCC. These reaction conditions were applied to the preparation of Merrifield resin-bound nitroacetate.
