2083-91-2Relevant articles and documents
Latent Nucleophilic Carbenes
Hurieva, Anastasiya,Koidan, Georgyi,Kostyuk, Aleksandr,Kyrylchuk, Andrii A.,Marchenko, Anatoliy,Rozhenko, Alexander B.,Rusanov, Eduard B.,Shvydenko, Kostiantyn
, (2021/12/27)
Using DFT and ab initio calculations, we demonstrate that noncyclic formamidines can undergo thermal rearrangement into their isomeric aminocarbenes under rather mild conditions. We synthesized the silylformamidine, for which the lowest activation energy in this process was predicted. Experimental studies proved it to serve as a very reactive nucleophilic carbene. The reactions with acetylenes, benzenes, and trifluoromethane proceeded via insertion into sp, sp2, and spCH bonds. The carbene also reacted with the functional groups, such as CHO, COR, and CN at double or triple bonds, displaying high mobility of the trimethylsilyl group. The obtained silylformamidine can be considered as a latent nucleophilic carbene. It can be prepared in bulk quantities, stored, and used when the need arises. Calculation results predict similar behavior for some other silylated formamidines and related compounds.
IMINE-TYPE QUATERNARY AMMONIUM SALT CATALYST, PREPARATION METHOD THEREOF AND USE THEREOF FOR PREPARATION OF POLYISOCYANATE COMPOSITION
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Paragraph 0021; 0057-0058; 0077-0078, (2020/12/13)
Disclosed is an imine-type quaternary ammonium salt catalyst, wherein the catalyst has a general structure formula shown by formula I below; in the formula, R1 and R2, respectively, are independently selected from a C1-C20 linear alkyl or a branched C3-C20 alkyl, and a C1-C20 hydroxylalkyl, a C3-C8 cycloalkyl, and arylated alkyl; R3 is a linear or branched alkyl, cycloalkyl or aryl; and R4 is hydrogen, aryl, a linear C1-C15 alkyl or branched C3-C15 alkyl. Also disclosed are a method for preparing the catalyst and a polyisocyanate composition prepared therefrom. The catalyst, by introducing an imine structure, on the basis of ensuring high catalytic activity thereof, is allowed to have properties of high temperature decomposition and inactivation, and when applied to the synthesis of polyisocyanate, can effectively prevent the risk of explosive polymerization caused by an uncontrolled reaction.
METHOD FOR PRODUCING DIALKYLAMINOSILANE
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Paragraph 0044-0048, (2018/03/09)
In a method for synthesizing dialkylaminosilane from a reaction of dialkylamine with chlorosilane as the method for producing dialkylaminosilane, a large amount of dialkylamine hydrochloride is produced as a by-product, in addition to objective dialkylaminosilane. Therefore, upon obtaining objective dialkylaminosilane, reduction of volumetric efficiency caused by a large amount of a solvent is prevented, and dialkylaminosilane is produced at a low cost and in a large amount. Dialkylaminosilane having a small halogen content is produced with high volumetric efficiency by using, as a solvent upon allowing dialkylamine to react with chlorosilane, an aprotic polar solvent having high solubility in dialkylamine hydrochloride and metal chloride each produced as a by-product by the reaction, and straight-chain or branched hydrocarbon having high solubility in dialkylaminosilane and hard to dissolve a halogen compound therein.
An Alumino-Mannich Reaction of Organoaluminum Reagents, Silylated Amines, and Aldehydes
Tarasewicz, Anika,Ensan, Deeba,Batey, Robert A.
supporting information, p. 6071 - 6074 (2018/04/27)
A multi-component coupling using organoaluminum reagents, silylated amines, and aldehydes results in the formation of tertiary amines. Both alkenyl- and alkylaluminum reagents undergo reaction with iminium ion substrates for which the corresponding Petasis borono-Mannich reactions are unsuccessful.
Organic [...] compound
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Paragraph 0069; 0070; 0071; 0072; 0073; 0074; 0075-0078, (2018/05/26)
This method for producing an organic silyl amine compound (3) represented by general formula (3) is characterized in that ammonia is removed by reactive distillation when an organic disilazane compound (1) represented by general formula (1) is reacted with an alkyl amine represented by general formula (2). An organic silyl amine compound can be obtained by this production method with high productivity without producing a salt. (In the formulae, each of R1, R2 and R3 independently represents a linear or branched alkyl group having 1-7 carbon atoms, a cyclic alkyl group having 3-5 carbon atoms or a phenyl group; and each of R4 and R5 independently represents a hydrogen atom, a linear or branched alkyl group having 1-5 carbon atoms or a cyclic alkyl group having 3-5 carbon atoms, provided that R4 and R5 are not hydrogen atoms at the same time.)
METHOD FOR PRODUCING SILYLAMINE
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Paragraph 0023; 0024; 0025; 0026, (2016/12/12)
PROBLEM TO BE SOLVED: To provide a method for producing a silylamine with higher efficiency and at lower cost than a conventional method. SOLUTION: There is provided a method for producing a silylamine in which R1R2R3SiNR4R5 is obtained by reacting a disilazane represented by R1R2R3SiNHSiR1R2R3 (provided that R1, R2 and R3 each independently represent an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms) and an amine represented by R4R5NH (provided that R4 and R5 each independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or a phenyl group) in the presence of a non-protonic highly polar solvent and a strong acid or an ammonium salt thereof. COPYRIGHT: (C)2015,JPOandINPIT
Reaction of iodo(trimethyl)silane with N,N-dimethyl carboxylic acid amides
Voronkov,Tsyrendorzhieva,Lis,Rakhlin
experimental part, p. 791 - 793 (2010/10/04)
The reactions of iodo(trimethyl)silane with N,N-dimethylformamide and N,N-dimethylacetamide Me2NCOR (R = H, Me) at a molar ratio of 1: 2 involved mainly cleavage of the N-C(=O) bond with formation of up to 80% of N,N-dimethyltrimethylsilylamine Me3SiNMe2 and the corresponding acyl iodide RCOI. In the reaction with N,N-dimethylformamide, formyl iodide HCOI was detected for the first time by gas chromatography-mass spectrometry. The contribution of Me-N bond cleavage, leading to N-methyl-N-trimethylsilyl derivative Me(Me3Si)NCOR and methyl iodide was considerably smaller. Another by-product was the corresponding N-methyl imide MeN(COR)2 formed by reaction of the initial amide with acyl iodide. The primary intermediate in the reaction of iodo(trimethyl)silane with DMF and DMA is quaternary ammonium salt [Me2(Me3Si)N +COR] I- which decomposes via dissociation of the N-CO and N-Me bonds.
A Simple and Highly Diastereoselective One-Pot Synthesis of Mannich-Bases
Arend, Michael,Risch, Nikolaus
, p. 974 - 976 (2007/10/03)
A convenient one-pot procedure for the synthesis of β-amino ketones 5 from economical shelf reagents is described. Iminium salts 3 are generated in virtually quantitative yields from secondary amines 1 and aldehydes 2 mediated by NaI/Me3SiCl/NEt3. Subsequently, the salts 3 are used for the in situ aminoalkylation of enamines 4. The method provides the Mannich bases 5 in high yields and excellent diastereoselectivities (>96 % ds). It can also be applied for the aminoalkylation of other nucleophiles such as imines or electron-rich aromatic compounds.
