Radical Additions of Tertiary Amines to Chlorotrifluoroethylene

Radical addition of ethyldimethylamine, cyclohexyldimethylamine, 1-methylpyrrolidine, 1-methylpiperidine, 1-methylperhydroazepine and 1-methylmorpholine to chlorotrifluoroethylene afforded 1 : 1 and 1 : 2 adducts containing 2-chloro-1,1,2-trifluoroethyl groups in the α- or α,α'-positions. Further reaction products were 1 : 2 telomers and secondary products arising by reduction of the chlorine atom in CHFCl groups by tertiary amines. The reaction course and mass and NMR spectra of the products are discussed.

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A study of reaction of aromatic polynitro compounds with tributylstannyl hydride

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19852598 ◽

1985 ◽

Vol 50 (11) ◽

pp. 2598-2606 ◽

Cited By ~ 4

Author(s):

Vladimír Macháček ◽

Antonín Lyčka ◽

Milan Nádvorník

Keyword(s):

Nmr Spectra ◽

Reaction Products ◽

Tetramethylammonium Bromide ◽

Composition And Structure

1H, 13C, 15N, and 119Sn NMR spectra have been used to study composition and structure of reaction products from 1,3,5-trinitrobenzene, methyl 2,4,6-trinitrobenzoate, 1-dimethylamino-2,4,6-trinitrobenzene, 1-methoxy-2,4,6-trinitrobenzene, 1-chloro-2,4,6-trinitrobenzene, 2,4,6-trinitrotoluene, 3,5-dinitrobenzonitrile and methyl 3,5-dinitrobenzoate with tributylstannyl hydride in the presence of tetramethylammonium bromide.

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A 15N, 13C, and 1H NMR study of reaction products from arylguanidines and chloroformate esters

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19911505 ◽

1991 ◽

Vol 56 (7) ◽

pp. 1505-1511 ◽

Cited By ~ 2

Author(s):

Antonín Lyčka ◽

Karel Palát

Keyword(s):

1H Nmr ◽

Nmr Spectra ◽

Reaction Products ◽

H Nmr ◽

Nmr Study

The 15N, 13C, and 1H NMR spectra of the reaction products from arylguanidines with two mols of chloroformate esters have been measured. With application of the corresponding 15N isotopomer it has been proved that the reaction products have the structures IIIa-IIIc.

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Mechanism and kinetics of radiolytically initiated cyclohexyl radical addition to cis- and trans-1,2-dichloroethylene and of the subsequent chlorine atom elimination reaction

Journal of the American Chemical Society ◽

10.1021/ja00709a036 ◽

1970 ◽

Vol 92 (6) ◽

pp. 1634-1637 ◽

Cited By ~ 5

Author(s):

Abraham. Horowitz ◽

L. A. Rajbenbach

Keyword(s):

Chlorine Atom ◽

Radical Addition ◽

Elimination Reaction ◽

Mechanism And Kinetics ◽

Cis And Trans ◽

Kinetics Of

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A Theoretical Study of Chlorine Atom and Methyl Radical Addition to Nitrogen Bases: Why Do Cl Atoms Form Two-Center−Three-Electron Bonds Whereas CH3Radicals Form Two-Center−Two-Electron Bonds?

Journal of the American Chemical Society ◽

10.1021/ja9613973 ◽

1996 ◽

Vol 118 (43) ◽

pp. 10571-10576 ◽

Cited By ~ 29

Author(s):

Michael L. McKee ◽

Athanassios Nicolaides ◽

Leo Radom

Keyword(s):

Chlorine Atom ◽

Theoretical Study ◽

Radical Addition ◽

Methyl Radical ◽

Nitrogen Bases ◽

Cl Atoms

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Nitration and bromination of l,1-diphenyl-2-(2-thienyl)ethylene

Canadian Journal of Chemistry ◽

10.1139/v78-454 ◽

1978 ◽

Vol 56 (21) ◽

pp. 2755-2757 ◽

Cited By ~ 6

Author(s):

Francesco A. Bottino ◽

Giuseppe C. Pappalardo ◽

Giuseppe Scarlata ◽

Domenico Sciotto ◽

Michele Torre

Keyword(s):

Dipole Moment ◽

Nmr Spectra ◽

Reaction Products ◽

H Nmr

The behaviour of 1,1-diphenyl-2-(2-thienyl)ethylene towards electrophilic agents (Br2, HNO3) has been investigated and the structure of reaction products assigned by uv, 1H nmr spectra, and dipole moment measurements.

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Photoreaktionen von Dekacarbonyldirhenium mit Allen und unverzweigten Allenderivaten / Photoreactions of Decacarbonyldirhenium with Allene and Unbranched Derivatives of Allene

Zeitschrift für Naturforschung B ◽

10.1515/znb-1995-0430 ◽

1995 ◽

Vol 50 (4) ◽

pp. 649-660 ◽

Cited By ~ 5

Author(s):

Cornelius G. Kreiter ◽

Wolfgang Michels ◽

Gerhard Heeb

Keyword(s):

Nmr Spectra ◽

Crystal And Molecular Structure ◽

Reaction Products ◽

X Ray Diffraction ◽

X Ray ◽

H Nmr ◽

Oxidative Rearrangement ◽

Dirhenium Complexes ◽

Derivatives Of ◽

By Products

Decacarbonyldirhenium (1) reacts upon UV irradiation with allene (2), 1,2-butadiene (3) and 2,3-pentadiene (4) preferentially by CO substitution and oxidative rearrangement to the corresponding enneacarbonyl-μ-η1:3-endiyl-dirhenium complexes 5, 9, and 15 and to the octacarbonyl-μ-η2:2-allene-dirhenium complexes 6, the stereoisomers 10, 11, and 16. At elevated temperature 5, 9, and 15 loose CO and yield by a reductive rearrangement also the complexes 6, 10, 11, and 16. In addition to these main products, depending upon the allene derivative used, various by-products are obtained.By-products of the reaction o f 1 with 2 are octacarbonyl-μ-η3:3-(2,3-dimethylene-buta-1,4- diyl)dirhenium (7) and μ-η2:2-allene-hexacarbonyl-μ-η1:3-1-propene-1,3-diyl-dirheniurn (8). The photo reaction of 1 with 3 yields, in addition to 9-11, tetracarbonyl-η3-(E-5-ethylidene- 4-methyl-2-cyclopenten-1-yl)rhenium (12) and tetracarbonyl-η3-(Z-5-ethyliden-4- methyl-2-cyclopenten-1-yl)rhenium (13) as a mixture of isomers. 1 and 4 form the by-products tetracarbonyl-η3-(EZ-3-penten-2-yl)rhenium (17), tetracarbonyl-η3-(EE-3-penten-2-yl)rhenium (18) and heptacarbonyl-μ-η1:2:1:2-(4,5-dimethyl-2,6-octadiene-3,6-diyl)dirhenium (19) with an unusually bridging and chelating ligand. The constitutions of the reaction products have been concluded from the IR and 1H NMR spectra. For 19 the crystal and molecular structure has been determined by X-ray diffraction analysis.

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Carbon-13 NMR Spectra of Some 6-Chloro-4-Hydroxy-2-Oxopyrano-3-Carboxyl Derivative, 7-Chloro-Pyrano-1, 3-Oxazine and their Morpholine Reaction Products

Spectroscopy Letters ◽

10.1080/00387018908054027 ◽

1989 ◽

Vol 22 (10) ◽

pp. 1313-1321

Author(s):

Jasim M. A. Al-Rawi ◽

Abdul-Hakim Th. Mahmood

Keyword(s):

Nmr Spectra ◽

Reaction Products ◽

Carboxyl Derivative

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Semiconductors as sensitisers for the radical addition of tertiary amines to electron deficient alkenes

International Journal of Photoenergy ◽

10.1155/s1110662x03000308 ◽

2003 ◽

Vol 5 (3) ◽

pp. 175-182 ◽

Cited By ~ 23

Author(s):

Siniša Marinković ◽

Norbert Hoffmann

Keyword(s):

Electron Transfer ◽

Organic Synthesis ◽

Radical Reaction ◽

Heterogeneous Photocatalysis ◽

Radical Addition ◽

Point Of View ◽

Tertiary Amines ◽

Radical Intermediate ◽

Radical Chain ◽

High Yields

Using heterogeneous photocatalysis, the radical addition of tertiary amines with electron deficient alkenes can be performed in high yields (up to 98%) and high facial diastereoselectivity. The photochemical induced electron transfer process initiates the radical chain reaction and inorganic semiconductors likeTiO2and ZnS were used. According to the proposed mechanism, the reaction takes place at the surface of the semiconductor and the termination step results from an interfacial electron transfer from the conduction band to the oxoallyl radical intermediate. Frequently, semiconductors are used for the mineralisation of organic compounds in wastewater. However, in this case, they are used in organic synthesis. The process can be performed in a convenient way and is particularly interesting from the ecological and economical point of view. No previous functionalization of the tertiary amines is necessary for C − C bond formation. Further on, the amines are used both as reactant and as solvent. The excess is recycled by distillation and the inexpensive sensitiser can be easily removed by filtration. In this way, products of high interest for organic synthesis are obtained by a diastereoselective radical reaction.

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