Hydrohalogenation of Unactivated Alkenes Using a Methanesulfonic Acid/Halide Salt Combination

Synthesis ◽  
2021 ◽  
Author(s):  
Jean-François Paquin ◽  
Xavier Bertrand ◽  
Pascal Paquin ◽  
Laurent Chabaud
Keyword(s):  
Acetic Acid ◽  
Methanesulfonic Acid ◽  
Alkyl Halides ◽  
Halide Salt ◽  
Acid Halide ◽  
Halide Salts

AbstractThe hydrochlorination, hydrobromination, and hydroiodination of unactivated alkenes using methanesulfonic acid and inorganic halide salts (CaCl2, LiBr, LiI) in acetic acid are reported. This approach uses readily available and inexpensive reagents to provide the alkyl halides in up to 99% yield. An example of deuteriochlorination using deuterated acetic acid as the solvent is also demonstrated.

scholarly journals NUCLEOPHILIC SUBSTITUTION REACTION OF CYANIDE AND METHOXYDE IONS TO QUATERNARY MANNICH BASE FROM VANILLIN

2010 ◽  
Vol 5 (3) ◽  
pp. 203-206
Author(s):  
Bambang Purwono ◽  
Estiana R. P. Daruningsih
Keyword(s):  
Nucleophilic Substitution ◽  
Mannich Reaction ◽  
Substitution Reaction ◽  
Mannich Base ◽  
Nucleophilic Substitution Reaction ◽  
Substitution Reactions ◽  
Halide Salt ◽  
Leaving Group ◽  
Dimethyl Amine ◽  
Halide Salts

The nucleophilic substitution reaction to quaternary Mannich base from vanillin has been investigated. Mannich reaction to vanillin was carried out by refluxing mixture of vanillin, formaldehyde and dimethyl amine. Quaternary ammonium halide salt was obtained from reaction of Mannich vanillin base with methyl iodide in THF solvents and yielded 93.28 %. Nucleophilic substituion to the halide salts with cyanide nucleophile produced 4-hidroxy-3-methoxy-5-(cyano)methylbenzaldehyde in 54.39% yield. Reaction with methoxyde ion yielded 4-hydroxy- 3-methoxy-5-(methoxy) -methylbenzaldehyde in 67.80% yield. The nucleophilic substitution reaction showed that trimethylamino substituent of quaternary Mannich base can act as a good leaving group on nucleophilic substitution reactions. Keywords: Mannich reaction, vanillin, nucleophilic substitution

scholarly journals Crystal structures of three halide salts of L-asparagine: an isostructural series

2018 ◽  
Vol 74 (11) ◽  
pp. 1619-1623 ◽  
Author(s):  
Lygia S. de Moraes ◽  
Alan R. Kennedy ◽  
Charlie R. Logan
Keyword(s):  
Hydrogen Bonds ◽  
Acid Amide ◽  
Water Molecules ◽  
Halide Ions ◽  
Carboxylic Acid Amide ◽  
Torsion Angles ◽  
Halide Salt ◽  
Halide Salts ◽  
Salt Forms ◽  
Chloride Monohydrate

The structures of three monohydrated halide salt forms of L-asparagine are presented, viz.L-asparaginium chloride monohydrate, C4H9N2O3 +·Cl−·H2O, (I), L-asparaginium bromide monohydrate, C4H9N2O3 +·Br−·H2O, (II), and L-asparaginium iodide monohydrate, C4H9N2O3 +·I−·H2O, (III). These form an isomorphous and isostructural series. The C—C—C—C backbone of the amino acid adopts a gauche conformation in each case [torsion angles for (I), (II) and (III) = −55.4 (2), −55.6 (5) and −58.3 (7)°, respectively]. Each cation features an intramolecular N—H...O hydrogen bond, which closes an S(6) ring. The extended structures feature chains of cations that propagate parallel to the b-axis direction. These are formed by carboxylic acid/amide complimentary O—H...O + N—H...O hydrogen bonds, which generate R 2 2(8) loops. These chains are linked by further hydrogen bonds mediated by the halide ions and water molecules to give a layered structure with cation and anion layers parallel to the ab plane. Compound (III) was refined as an inversion twin.

Application of the Sulfuric Acid-Halide Salt Reaction to the Analysis of Sulfuric Acid Containing Aerosols

1980 ◽  
Vol 13 (16) ◽  
pp. 1397-1408 ◽  
Author(s):  
D. Klockow ◽  
R. Nießner ◽  
B. B. Jablonski
Keyword(s):  
Sulfuric Acid ◽  
Halide Salt ◽  
Acid Halide

Hydration of Some Acids in Sulfolane

1975 ◽  
Vol 53 (18) ◽  
pp. 2683-2688 ◽  
Author(s):  
R. L. Benoit ◽  
S. Y. Lam
Keyword(s):  
Acetic Acid ◽  
Sulfonic Acid ◽  
Picric Acid ◽  
Methanesulfonic Acid ◽  
Pressure Measurements ◽  
Methane Sulfonic Acid ◽  
Enthalpy Changes ◽  
Low Concentrations ◽  
Vapor Pressure Measurements ◽  
And Calorimetry

Interaction between water at low concentrations and some carboxylic acids, methane-sulfonic acid and picric acid, HA, have been studied in Sulfolane at 30 °C. Vapor pressure measurements and calorimetry were used. Results are interpreted in terms of hydration constants K1 and enthalpy changes ΔH1, for the 1:1 complexes [Formula: see text] The values of K1 are low and generally increase slightly with the strength of the acid HA from ∼0.4 for acetic acid to 5.7 for methanesulfonic acid.

scholarly journals NUCHLEOPHILIC SUBSTITUTION REACTION OF CYANIDE AND METHOXYDE IONS TO QUATERNARY MANNICH BASE FROM VANILLIN

2010 ◽  
Vol 7 (1) ◽  
pp. 58-60
Author(s):  
Bambang Purwono ◽  
Estiana E.P Daruningsih
Keyword(s):  
Nucleophilic Substitution ◽  
Mannich Reaction ◽  
Quaternary Ammonium ◽  
Substitution Reaction ◽  
Mannich Base ◽  
Nucleophilic Substitution Reaction ◽  
Nucleophilic Reaction ◽  
Halide Salt ◽  
Dimethyl Amine ◽  
Halide Salts

The nucleophilic substitution reaction to quaternary Mannich base from vanillin has been investigated. Mannich reaction to vanillin was carried out by refluxing mixture of vanillin, formaldehyde and dimethyl amine. Quaternary ammonium halide salt was obtained from reaction of Mannich vanillin base with methyl iodide in THF solvents and yielded  93.28%. Nucleophilic substituion to the halide salts with cyanide nucleophile produced 4-hidroxy-3-methoxy-5-(cyano)methylbenzaldehyde in 54.39% yield, with methoxyde ion obtained  4-hidroxy- 3-methoxy-5-(methoxy)-methyl-benzaldehide in 67.80% yield. The nucleophilic substitution reaction showed that substituen of trimethylamino quaternary Mannich base can act as a good leaving on nucleophilic reaction substitutions.   Keywords: Mannich Reaction, Vanillin, nucleophilic substitution.

scholarly journals A Mechanistic Study on the Formation of Dronic Acids

Molecules ◽  
2021 ◽  
Vol 26 (24) ◽  
pp. 7587
Author(s):  
Péter Ábrányi-Balogh ◽  
István Greiner ◽  
György Keglevich
Keyword(s):  
Acetic Acid ◽  
Quantum Chemical ◽  
Methanesulfonic Acid ◽  
Phosphorous Acid ◽  
Bone Diseases ◽  
Phosphorus Trichloride ◽  
Mechanistic Study ◽  
First Variation ◽  
The First Variation ◽  
High Level

Dronic acid derivatives, important drugs against bone diseases, may be synthesized from the corresponding substituted acetic acid either by reaction with phosphorus trichloride in methanesulfonic acid as the solvent or by using also phosphorous acid as the P-reactant if sulfolane is applied as the medium. The energetics of the two protocols were evaluated by high-level quantum chemical calculations on the formation of fenidronic acid and benzidronic acid. The second option, involving (HO)2P‑O‑PCl2 as the nucleophile, was found to be more favorable over the first variation, comprising Cl2P‑O‑SO2Me as the real reagent, especially for the case of benzidronate.

scholarly journals Theoretical and Practical Considerations of the Newer Methods of the European Pharmacopeia for the Assay of Halide Salts of Organic Bases

2002 ◽  
Vol 70 (2) ◽  
pp. 129-133 ◽  
Author(s):  
Keyword(s):  
Hydrochloric Acid ◽  
Sodium Hydroxide ◽  
Potentiometric Titration ◽  
Halide Salt ◽  
Organic Bases ◽  
Halide Salts

A certain type of titration methods have appeared with an increasing frequency during the last years, this being evident surveying the latest editions of the European Pharmacopeia (1997-2001) [1-3], where there are now more than fifty monographs on the assay of halide salt of organic bases by potentiometric titration of the sample dissolved in ethanol or in an ethanolwater mixture with sodium hydroxide after addition of a defined volume of diluted hydrochloric acid [...]

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