- A novel deacylation during the amination of trifluoromethyl β-dicarbonyl compounds
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Starting from trifluoromethyl β-dicarbonyl compounds, a rare loss of CF3CO was observed in the amination reactions performed under heterogeneous conditions using NsONHCO2Et as the aminating agent and CaO or NaH as the base, while corresponding nonfluorinated β-dicarbonyl compounds under analogous conditions give non deacylated aminated compounds. This reaction can facilitate a direct synthesis of N-substituted α-amino esters or α-amino ketones.
- Fioravanti, Stefania,Pellacani, Lucio,Ramadori, Federico,Tardella, Paolo A.
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- Method for preparing 3-(3-chloropropyl)-4-oxopyrrolidin-1-carboxylate
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The invention provides a method for preparing 3-(3-chloropropyl)-4-oxopyrrolidin-1-carboxylate (I). The method comprises the steps: subjecting glycinate or an acceptable salt thereof (VIII), which serves as a raw material, to a reaction with chloroformate (VII), so as to produce an intermediate ethoxycarbonyl glycinate (VI); subjecting the intermediate (VI) to cyclization with acrylate (V) under alkaline conditions, so as to obtain a pyrrolidone intermediate (IV); and subjecting the intermediate (IV) to a reaction with 1,3-halochloropropane (III) so as to obtain an intermediate (II), and then,carrying out decarboxylation under acidic conditions, thereby obtaining the 3-(3-chloropropyl)-4-oxopyrrolidin-1-carboxylate (I). Compared with old processes, the method has the advantages that processing steps are shortened, processing operations are simplified, and the emission of waste gases, waste water and waste residues and the cost are greatly reduced, thereby being beneficial to industrialized enlarged production.
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Paragraph 0040
(2020/02/19)
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- Titanium(IV) Complexes Based on Tridentate N,N,O Ligands - Synthesis, Structure, and Thermal Decomposition
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New tridentate N,N,O-type ligands MeN(CH2CH2NHTs)(CH2CR2OH) [Ts = tosyl; R = H, 6, (N,N,OH)H2; R = Ph, 7 (N,N,OPh)H2] were prepared. The corresponding diisopropoxide c
- Cherepakhin, Valeriy S.,Zaitsev, Kirill V.,Oprunenko, Yuri F.,Churakov, Andrei V.,Lermontova, Elmira Kh.,Zaitseva, Galina S.,Karlov, Sergey S.
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p. 5903 - 5912
(2015/12/24)
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- Base-promoted c→n acyl rearrangement: An unconventional approach to α-amino acid derivatives
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We have discovered that N-alkyl aminomalonates undergo a fast and selective intramolecular C→N acyl rearrangement reaction in the presence of a strong base, leading to N-protected glycinates in excellent yield. Moreover, the fact that the reaction proceeds through a nucleophilic enolate intermediate has been used for implementing a tandem rearrangement/alkylation sequence that has been applied to the preparation of synthetically relevant nonproteinogenic tertiary and quaternary N-alkyl α-amino acids in a very simple and reliable way.
- Ugarriza, Iratxe,Uria, Uxue,Carrillo, Luisa,Vicario, Jose L.,Reyes, Efraim
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supporting information
p. 11650 - 11654
(2014/10/15)
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- Alkyl 1-Chloroalkyl Carbonates: Reagents for the Synthesis of Carbamates and Protection of Amino Groups
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The synthesis of 1-chloroalkyl carbonates and their reaction with various type of amines are described.This reaction is useful for the synthesis of carbamate pesticides and for the protection of various amino groups, including amino acids.
- Barcelo, Gerard,Senet, Jean-Pierre,Sennyey, Gerard,Bensoam, Jean,Loffet, Albert
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p. 627 - 632
(2007/10/02)
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- Orthoamides, XXXVIII. - Contributions to the Chemistry of Orthocarbonic Acid Esters and α,α,α-Trialkoxyacetonitriles
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The reactivity of the orthocarbonates 4 and the nitriles 1 has been investigated.Carboxylic acids are esterified by 4b. Orthocarbonates 4c-f and 9b are prepared by transesterification of 4b.Mixed substituted orthocarbonates 8c-f are obtained from the nitriles 1a,b.The nitriles 2a and 3a react with alkali alcoholate in alcohol to yield the orthocarbamic acid esters 13a,b. Spirocyclic orthocarbonates 17a-d are prepared from 4b and 1,2 or 1,3-dioles, respectively. The reaction of phenol with 1b affords the mixed substituted orthocarbonate 18a. Catechol is converted by 1a into the orthocarbonate 20a.Reactions of 4b with amines and ami ne derivatives are studied. In the course of these investigations guanidines 21, imidocarbonic acid esters 22a-c, 30, carbamic acid esters 25, ureas 26, the isourea derivative 29, as well as the 1,3,4-oxadiazole 31 are prepared. The mechanism of these reactions is discussed. Imidocarbonic acid esters 22d-f, 38, N-cyanocarbamates 39, and isoureas 37 can be prepared from 1b and amines or amine derivatives. 2a as well as 13b react with cyanamide to give the N-cyanoisourea 40. Ureas 26 are formed in the reaction of 1a,b with secondary amines at elevated temperatures.The guanidinium cyanide 41a can be obtained by reaction of pyrrolidine with 1b in ether, whereas under similiar conditions from 1a and pyrrolidine the amidine 42 is produced. o-Aminophenol, o-phenylenediamine and anthranilic acid are cyclized by 4b or 1b to afford the heterocyclic compounds 43-45. α- and β-amino acids are transformed by 4b or 1b into the N-(ethoxycarbonyl)amino acid esters 46 and 47, respectively.
- Kantlehner, Willi,Maier, Thomas,Loeffler, Wolfgang,Kapassakalidis, Joanis J.
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p. 507 - 529
(2007/10/02)
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