109-69-3Relevant articles and documents
-
Squires et al.
, p. 134 (1975)
-
Catalytic decomposition of alkyl chloroformates by hexabutylguanidinium chloride
Foulon, Frederique,Fixari, Bernard,Picq, Dominique,Le Perchec, Pierre
, p. 3387 - 3390 (1997)
Hexabutylguanidinium chloride (0.5 molar %) efficiently decomposes alkyl chloroformates into chlorides, with low alkenes formation, via a S(N)2 mechanism as demonstrated from substituents effects and asymmetric chloride synthesis.
-
Toptschijew
, p. 185,187 (1955)
-
Improvements in the Hexachloroacetone/Triphenylphosphine Procedure for the Conversion of Allylic Alcohols into Chlorides
Magid, Ronald M.,Talley, Brenda G.,Souther, Stephen K.
, p. 824 - 825 (1981)
-
Crystal Growth of Alkali-metal Halides during Gas-liquid Phase-transfer Catalysis
Angeletti, Enrico,Tundo, Pietro,Venturello, Paolo,Rubo, Marco
, p. 493 - 496 (1983)
The alkali-metal halide crystals produced during an organic synthesis carried out under gas-liquid phase-transfer catalysis (g.l.-p.t.c.) conditions grow in an unusual liquid medium by consuming the nucleophile salt; their habit depends on the catalyst used and on the reaction considered.The particular crystal habit, showing a cavity on one face only of the cube or on one corner only of the octahedron, illustrates some aspects of the crystal growth and gives information on g.l.-p.t.c. mechanism.
-
Fuchs,Cole
, p. 3620 (1975)
-
Layered Double Hydroxides as Supported Anionic Reagents. Halide Ion Reactivity in X*nH2O
Martin, Kevin J.,Pinnavaia, Thomas J.
, p. 541 - 542 (1986)
-
-
Bailey,Prest
, p. 1,2 (1971)
-
SN2 Reactions in the Gas Phase. Temperature Dependence of the Rate Constants and Energies of the Transition States. Comparison with Solution
Caldwell, Gary,Magnera, Tom F.,Kebarle, Paul
, p. 959 - 966 (1984)
The rate constants for the gas-phase reactions Cl- + RBr = ClR + Br-, where R = Me, Et, n-Bu, i-Pr, and i-Bu, were determined for temperatures between 25 and 390 deg C with a pulsed electron beam high ion source pressure mass spectrometer.The rate constants for Me decreased with an increase of temperature (negative temperature dependence).Et and n-Bu had almost no temperature dependence while i-Pr and i-Bu had positive temperature dependence.An analysis of the data on the basis of theory provides approximate values for ΔE0, the energy of the transition state relative to the energy of the reactants.These ΔE0 values are as follows: Me, -2.5; Et, 0.8; n-Bu, -0.5; i-Pr, +5.1; i-Bu, +5.7 kcal/mol.The δΔE0 are compared with relative activation energies: δEa in solution (C.K.Ingold and A.J.Parker) and calculated strain energies δΔEstrain due to steric repulsions in the transition state (C.K.Ingold and D.F.DeTar).An approximate agreement between the three sets of data is found.This finding supports the assumption of Ingold that steric effects in the transition state dominate the relative rates of this reaction series.The temperature dependence of the rate constants in the gas phase is of interest to ion-molecule reaction theory.It provides a graphic demonstration for the effect of the central barrier in the double-well reaction coordinate.When ΔE0 is negative, negative temperature dependence is observed.When -ΔE0 is small (Me, n-Bu) the reaction proceeds with chemical activation at the very low pressures used in ion cyclotron resonance but with near Boltzmann transition-state distribution at the higher pressures used in high-pressure mass spectrometry.When ΔE0 is positive, the reaction proceeds with positive temperature dependence and boltzmann transition-state distribution.
Wijnen, M. H. J.
, p. 3014 - 3017 (1961)
-
Drahowzal,Klamann
, p. 970,974 (1951)
-
Preparation method of 1-chlorobutane
-
Paragraph 0039-0058, (2021/04/28)
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a preparation method of 1-chlorobutane. A reaction solvent, water and n-butyl alcohol are mixed, and a chlorination reagent is added for reaction to obtain 1-chlorobutane, wherein the reaction solvent is 2, 3, 5, 6-tetramethyl dioxane. A one-pot method is adopted, and the method is simple, good in safety, easy to implement, low in equipment requirement and capable of realizing continuous production. The problem of heavy pollution of the traditional metal catalyst is avoided, three wastes are few, and the method is environment-friendly. 2, 3, 5, 6-tetramethyl dioxane is used as a reaction solvent and a catalyst, so that the generation of byproducts such as butene, dibutyl ether and polymer resin can be effectively avoided, the yield and the product quality are improved, the molar yield of the product is 96% or above, and the gas phase purity is 99.7% or above.
Palladium-Catalyzed Decarbonylative Iodination of Aryl Carboxylic Acids Enabled by Ligand-Assisted Halide Exchange
Boehm, Philip,Cacherat, Bastien,Lee, Yong Ho,Martini, Tristano,Morandi, Bill
supporting information, p. 17211 - 17217 (2021/07/02)
We report an efficient and broadly applicable palladium-catalyzed iodination of inexpensive and abundant aryl and vinyl carboxylic acids via in situ activation to the acid chloride and formation of a phosphonium salt. The use of 1-iodobutane as iodide source in combination with a base and a deoxychlorinating reagent gives access to a wide range of aryl and vinyl iodides under Pd/Xantphos catalysis, including complex drug-like scaffolds. Stoichiometric experiments and kinetic analysis suggest a unique mechanism involving C?P reductive elimination to form the Xantphos phosphonium chloride, which subsequently initiates an unusual halogen exchange by outer sphere nucleophilic substitution.
Unexpected distinction in reactivity of pentafluorobenzenesulfonyl halides toward organolithiums and organomagnesium halides
Bardin, Vadim V.,Maksimov, Alexander M.
, p. 731 - 737 (2017/10/16)
C6F5SO2Cl reacts with organolithiums and organomagnesium halides RM (R = Me, Bu, Ph; M = Li, MgX) to give mainly C6F5H and C6F5Cl. C6F5SO2Br and
