27 research outputs found
Analysis of ergonomics problems contact-centers
The analysis of the ergonomic problems
of the contact center. It allocates main factors of
influence on man- operator
On the Surface-Catalyzed Reaction between the Gases 2,2-Dimethylpropanal and Methanamine. Formation of Active-Site Imines
The reaction that occurs when vapors of 2,2-dimethylpropanal and methanamine are allowed to mix in
an infrared gas cell has been examined. The disappearance of starting materials and formation of E-imine
product, monitored simultaneously, is best fit by a process involving wall-associated water. The same or
closely related processes have been successfully modeled; such processes may also be common to
pyridoxal-catalyzed transamination and related reactions in biological systems
Second-Chance Rearrangement Route to Novel 5(6)-Syn,anti-difunctional 2-Azabicyclo[2.1.1]hexanes
The first syntheses of 5,6-difunctionalized-2-azabicyclo[2.1.1]hexanes containing syn-hydroxy and syn-fluoro substituents have been effected
in a stereocontrolled manner. The key reactions are regioselective additions to the aziridinium ions formed from 6-exo-iodo(bromo)-5-endo-X-2-azabicyclo[2.2.0]hexanes (X = F, OH) upon silver or mercury salt enhancement of iodide nucleofugacity
The Rearrangement Route to 3-CH<sub>2</sub>X-2-azabicyclo[2.1.1]hexanes. Substituent Control of Neighboring Group Participation
The stereocontrolled synthesis of a functionalized 3-hydroxymethyl-2-azabicyclo[2.1.1]hexane synthon for a variety of methano-bridged pyrrolidines
has been effected. The key step in an electrophilic addition−rearrangement route uses a 3-nosyloxymethyl group in the 2-azabicyclo[2.2.0]hex-5-ene precursor in order to suppress unwanted competitive oxygen neighboring group participation
Complex-Induced Proximity Effects. Temperature-Dependent Regiochemical Diversity in Lithiation−Electrophilic Substitution Reactions of <i>N</i>-BOC-2-Azabicyclo[2.1.1]hexane. 2,4- and 3,5-Methanoprolines
Azabicycle 4 and sec-butyllithium/TMEDA afford the C1 bridgehead α-lithio anion at 0 °C. Anion quenching with carbon dioxide, methyl
chloroformate, or DMF provide the bridgehead acid 8a (N-BOC-2,4-methanoproline), ester 8b, or aldehyde 8c, respectively. By contrast, at −78
°C these same reagents give a mixture of regioisomeric methylene and bridgehead anions whose quenching leads to mixtures of regioisomeric
methylene and bridgehead acids 6a/8a, esters 6b/8b, or aldehydes 6c/8c, respectively. The previously unknown 3,5-methanoproline was prepared
as its N-BOC methyl ester 6b
Complex-Induced Proximity Effects. Temperature-Dependent Regiochemical Diversity in Lithiation−Electrophilic Substitution Reactions of <i>N</i>-BOC-2-Azabicyclo[2.1.1]hexane. 2,4- and 3,5-Methanoprolines
Azabicycle 4 and sec-butyllithium/TMEDA afford the C1 bridgehead α-lithio anion at 0 °C. Anion quenching with carbon dioxide, methyl
chloroformate, or DMF provide the bridgehead acid 8a (N-BOC-2,4-methanoproline), ester 8b, or aldehyde 8c, respectively. By contrast, at −78
°C these same reagents give a mixture of regioisomeric methylene and bridgehead anions whose quenching leads to mixtures of regioisomeric
methylene and bridgehead acids 6a/8a, esters 6b/8b, or aldehydes 6c/8c, respectively. The previously unknown 3,5-methanoproline was prepared
as its N-BOC methyl ester 6b
The Rearrangement Route to 2-Azabicyclo[2.1.1]hexanes. Solvent and Electrophile Control of Neighboring Group Participation
The reactions of N-(alkoxycarbonyl)-2-azabicyclo[2.2.0]hex-5-enes 5 with halonium ion electrophiles
were studied in polar and nonpolar aprotic solvents and also in protic media with the aim of
controlling nitrogen neighboring group participation. Specifically, for bromonium ions nitrogen
participation is facilitated by the polar aprotic solvent nitromethane and by the poorly nucleophilic
protic solvent acetic acid. Alkene 5b and bromine/nitromethane afford only the rearranged anti,anti-5,6-dibromo-2-azabicyclo[2.1.1]hexane 6b, and NBS/acetic acid gives an 8:1 mixture favoring
rearranged 5-bromo-6-acetate 6f. Conversely, pyridinium bromide perbromide/CH2Cl2 is selective
for only unrearranged 5,6-dibromide 7. Iodonium and phenylselenonium ions react with alkenes 5
to give only unrearranged 1,2-addition products 9 and 10, regardless of solvent. Chloronium and
fluoronium ions react with alkenes 5 to give 4-aminomethyl-3-hydroxycyclobutene 11, derived by
ring cleavage
5(6)-<i>anti</i>-Substituted-2-azabicyclo[2.1.1]hexanes: A Nucleophilic Displacement Route
Nucleophilic displacements of 5(6)-anti-bromo substituents in 2-azabicyclo[2.1.1]hexanes (methanopyrrolidines) have been accomplished. These displacements have produced 5-anti-X-6-anti-Y-difunctionalized-2-azabicyclo[2.1.1]hexanes containing bromo, fluoro, acetoxy, hydroxy, azido, imidazole, thiophenyl, and iodo substituents. Such displacements of anti-bromide ions require an amine nitrogen and are a function of the solvent and the choice of metal salt. Reaction rates were faster and product yields were higher in DMSO when compared to DMF and with CsOAc compared to NaOAc. Sodium or lithium salts gave products, except with NaF, where silver fluoride in nitromethane was best for substitution by fluoride. The presence of electron-withdrawing F, OAc, N3, Br, or SPh substituents in the 6-anti-position slows bromide displacements at the 5-anti-position
5(6)-<i>anti</i>-Substituted-2-azabicyclo[2.1.1]hexanes: A Nucleophilic Displacement Route
Nucleophilic displacements of 5(6)-anti-bromo substituents in 2-azabicyclo[2.1.1]hexanes (methanopyrrolidines) have been accomplished. These displacements have produced 5-anti-X-6-anti-Y-difunctionalized-2-azabicyclo[2.1.1]hexanes containing bromo, fluoro, acetoxy, hydroxy, azido, imidazole, thiophenyl, and iodo substituents. Such displacements of anti-bromide ions require an amine nitrogen and are a function of the solvent and the choice of metal salt. Reaction rates were faster and product yields were higher in DMSO when compared to DMF and with CsOAc compared to NaOAc. Sodium or lithium salts gave products, except with NaF, where silver fluoride in nitromethane was best for substitution by fluoride. The presence of electron-withdrawing F, OAc, N3, Br, or SPh substituents in the 6-anti-position slows bromide displacements at the 5-anti-position
Selectfluor as a Nucleofuge in the Reactions of Azabicyclo[<i>n</i>.2.1]alkane β-Halocarbamic Acid Esters (<i>n</i> = 2,3)
The ability of Selectfluor to act as a nucleofuge for hydrolysis of β-anti-halides was investigated with
N-alkoxycarbonyl derivatives of 6-anti-Y-7-anti-X-2-azabicyclo[2.2.1]heptanes and 4-anti-Y-8-anti-X-6-azabicyclo[3.2.1]octanes. The azabicycles contained X = I or Br groups in the methano bridge and Y
= F, Br, Cl, or OH substituents in the larger bridge. The relative reactivities of the halides were a function
of the azabicycle, the halide, and its bridge and the addition of Selectfluor or HgF2 as a nucleofuge. All
halide displacements occurred with retention of stereochemistry. Selectfluor with sodium bromide or
sodium chloride, but not sodium iodide, competitively oxidized some haloalcohols to haloketones. A
significant 15.6 Hz F···HO NMR coupling was observed with 4-anti-fluoro-8-anti-hydroxy-6-azabicyclo[3.2.1]octane
