2019-71-8

Upstream product

• 128721-75-5 Te-butyl N,N-dimethylcarbamotelluroate 
• 100-52-7 benzaldehyde 
• 93799-43-0 mandelic acid N-hydroxysuccinimido ester 
• 124-40-3 dimethyl amine 
• 73764-14-4 N,N-dimethyl-2-phenyl-2-diazoacetamide 
• 611-71-2 MANDELIC ACID 
• 119-61-9 benzophenone 
• 68-12-2 N,N-dimethyl-formamide 
• 479486-96-9 N,N-dimethyl (trimethylsilyl)methanamide 
• 56043-45-9 N,N,N',N'-tetramethylchlorformamidinium chloride 
• 27032-85-5 5-phenyl-1,3-dioxalan-4-one 
• 51804-83-2 N,N-diisopropyl-2-oxo-2-phenylacetamide 

Downstream Products

• 917077-20-4 N,N-dimethyl-2-phenyl-2-(trimethylsilyloxy)acetamide 
• 51579-87-4 N,N-dimethyl-2-oxo-2-phenylacetamide 

Relevant academic research and scientific papers

Fluoroalkylation of Various Nucleophiles with Fluoroalkyl Sulfones through a Single Electron Transfer Process

The fluoroalkylation of various nucleophilic reagents with (phenylsulfonyl)difluoromethyl (PhSO2CF2)-substituted phenanthridines was achieved to give fluorinated phenanthridine derivatives, which enables the construction of both carbon-heteroatom and carbon-carbon bonds via the substitution of the phenylsulfonyl group. Mechanistic studies indicated that these reactions proceed through a unimolecular radical nucleophilic substitution (SRN1) mechanism. It is worthwhile noting that in the cases of O-nucleophiles (t-BuO- and PhO-), the addition of t-BuOK/PhCHO could significantly promote the reactions, due to the in situ formation of a highly reactive electron donor species through the interaction of t-BuOK, PhCHO, and the solvent DMF, which can effectively initiate the single electron transfer process.

Cross-benzoin and Stetter-type reactions mediated by KO: T Bu-DMF via an electron-transfer process

The condensation of aromatic α-diketones (benzils) with aromatic aldehydes (benzoin-type reaction) and chalcones (Stetter-type reaction) in DMF in the presence of catalytic (25 mol%) KOtBu is reported. Both types of umpolung processes proceed with good efficiency and complete chemoselectivity. On the basis of spectroscopic evidence (MS analysis) of plausible intermediates and literature reports, the occurrence of different ionic pathways have been evaluated to elucidate the mechanism of a model cross-benzoin-like reaction along with a radical route initiated by an electron-transfer process to benzil from the carbamoyl anion derived from DMF. This mechanistic investigation has culminated in a different proposal, supported by calculations and a trapping experiment, based on double electron-transfer to benzil with formation of the corresponding enediolate anion as the key reactive intermediate. A mechanistic comparison between the activation modes of benzils in KOtBu-DMF and KOtBu-DMSO systems is also described.

Orthoamides and iminium salts LXXIV [1]. Reactions of N,N,N',N'- Tetramethyl-chloroformamidiniumChloride with metals

N,N,N',N'-Tetramethyl-formamidinium chloride (2a) reacts with elemental sodium in various solvents to give N,N,N',N',N'',N''-hexamethyl-guanidinium chloride (4a). The reaction of 2a with potassium affords N,N,N',N',N'',N'',N''', N'''-octamethyl-oxamidinium dichloride (3a). From the reaction of 2a with magnesium in different solvents in general result mixtures of the salts 4a, 3a and N,N,N',N'-tetramethyl-formamidinium chloride (10a). The composition of these mixtures depends on the solvent and the reaction temperature. Similar results are obtained, when a zinc'copper couple is used instead of magnesium. Very likely from 2a and magnesium or zinc, respectively, organometallic intermediates 11, 12 are formed which could be trapped by aromatic aldehydes and phenylisocyanate. The salt 2a can be reductively coupled by a low-valent titanium reagent to give the oxamidinium salt 3a.

Tribromogermyl monochelates - Derivatives of N,N-disubstituted 2-hydroxycarboxylic amides

Reactions of GeBr4 with N,N-dimethyl-2- trimethylsiloxypropionamide (2a), (S)-2-trime-thylsiloxypropionpyrrolidide ((S)-2b), and N,N-dimethyl-O-(trimethylsilyl)mandelamide (2c) afforded pentacoordinated neutral (O,O)-monochelates, viz., N,N-dimethyl-2-tribromoger- myloxypropionamide (3a), (S)-2-tribromogermyloxypropionpyrrolidide ((S)-3b), and N,N-dimethyl-O-(tribromogermyl)mandelamide (3c), respectively. X-ray diffraction study was performed for tribromides 3a, (S)-3b, and 3c, as well as for the N,N-dimethylmandelamide (1c) described earlier. According to the X-ray diffraction data, the Ge atom in tribromides 3a, (S)-3b, and 3c is pentacoordinated and has trigonal bipyramidal configuration with two halogen atoms and oxygen atom of the ether group in the equatorial positions and the halogen atom and the amide oxygen atom in the axial fragment, the bonds in which are somewhat longer as compared to the analogous bonds in tetracoordinated Ge compounds.

O,O-Monochelate complexes of silicon and germanium halides: The derivatives of l-mandelic N,N-dimethylamide

Reactions of O-trimethylsilyl-l-mandelic N,N-dimethylamide (1) with tetrachlorosilane and tetrachlorogermane lead to O,O-monochelate complexes, [1-(dimethylcarbamoyl)-1-phenylmethoxy]trichlorosilane (2) and [1-(dimethylcarbamoyl)-1-phenylmethoxy]trichloro

Medium effects on Zwitterionic-biradicaloid intermediates from two phenyl-α-oxoamides. Irradiations in fluid and solid protic media, neat solid phases, and the solid, smectic and isotropic phases of a completely saturated phosphonium salt at different tem

The photochemical processes of two N,N-dialkyl phenyl-α-oxoamides, N,N-diisopropyl phenyl-α-oxoamide (1) and N,N-dibenzyl phenyl-α-oxoamide (2), are investigated at different temperatures in methanol and ethylene glycol (to probe the influences of H-bondi

Carbmoyllithiums. A Novel Method for Generation by Lithium-Tellurium Exchange Reaction

Reaction of Te-butyl carbamotelluroates with butyllithium at low temperatures resulted in efficient transmetallation to give corresponding carbamoyllithiums.A convenient one-pot procedure for nucleophilic carbamoylation using carbamoyl halides has been developed as an application of this reaction.

Reactions of α-Hydroxy Carbonyl Compounds with Azodicarboxylates and Triphenylphosphine: Synthesis of α-N-Hydroxy Amino Acid Derivatives

Reaction of aliphatic α-hydroxy esters with azodicarboxylates and triphenylphosphine in the presence of either CbzNHOCH2Ph or trOCNHOCH2Ph provides a direct route to protected α-N-hydroxy amino acids.Similar reactions with aromatic α-hydroxy carbonyl compounds and derivatives result in predominate oxidation to the corresponding α-oxo carbonyl derivatives.

187. Primary and Secondary Isotope Effects on Proton Transfers to Diazocarbonyl Compounds

The primary solvent isotope effects on the ASE-2 type hydrolyses of α-diazocarbonyl compounds p-XC6H4CN2CO2CH3 (X=NO2, H, OCH3 and C6H5CN2CON(CH3)2) are found to be identical despite large differences in their overall hydrolysis rates.The secondary solvent isotope effects diminish considerably with diminishing substrate reactivity, and for two substrates they are smaller than those normally anticipated for a simple proton transfer from the lyonium species.An analysis is presented of these and other abnormal secondary isotope effects found elsewhere, involving consideration of the solvation of the reaction complex.