The Application of Dichloromethane and Chloroform as Reagents in Organic Synthesis

Tlili, Anis; Schranck, Johannes

doi:10.1002/9783527805624.ch4

Cited by 11 publications

(10 citation statements)

References 139 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, the close relative compound of chloroform, dichloromethane is extensively applied in pharmaceutical and food industry, for e.g. in the decaffeination of coffee and tea and in the extraction of different flavorings [20]. Cerebrosides originating from fungi are conserved structures which consist of a ceramide portion with 9-methyl-4,8-sphingadienine in amidic linkage to 2-hydroxyoctadecanoic or 2-hydroxyhexadecanoic acids, and a carbohydrate moiety, namely glucose or galactose.…”

Section: Resultsmentioning

confidence: 99%

Cerebrosides and Steroids from the Edible Mushroom Meripilus giganteus with Antioxidant Potential

et al. 2020

View full text Add to dashboard Cite

The detailed chemical analysis of the methanol extract of Meripilus giganteus (Pers.) P. Karst. led to the isolation of two new cerebrosides, mericeramides A (1) and B (2) together with cerebroside B (3), ergosterol (4), 3β-hydroxyergosta-7,22-diene (5), cerevisterol (6), 3β-hydroxyergosta-6,8(14),22-triene (7), 3β-O-glucopyranosyl-5,8-epidioxyergosta-6,22-diene (8) and (11E,13E)-9,10-dihydroxy-11,13-octadecadienoic acid (9). The structures of the compounds were determined on the basis of NMR and MS spectroscopic analysis. Mericeramide A (1) is the first representative of halogenated natural cerebrosides. The isolated fungal metabolites 1–9 were evaluated for their antioxidant activity using the oxygen radical absorbance capacity (ORAC) assay. Compounds 2, 5 and 9 proved to possess considerable antioxidant effects, with 2.50 ± 0.29, 4.94 ± 0.37 and 4.27 ± 0.05 mmol TE/g values, respectively. The result obtained gives a notable addition to the chemical and bioactivity profile of M. giganteus, highlighting the possible contribution of this species to a versatile and balanced diet.

show abstract

Section: Resultsmentioning

confidence: 99%

Cerebrosides and Steroids from the Edible Mushroom Meripilus giganteus with Antioxidant Potential

et al. 2020

View full text Add to dashboard Cite

show abstract

“… 8 For instance, DCM can be used simultaneously as solvent and reagent, and due to its low boiling point and its poor miscibility with water and aqueous mixtures, it can be readily separated from polar or heavier substances and recycled for further uses. 9 Among others, clean chlorine substitution in DCM could lead to significant improvements in the syntheses of a wide variety of methylene-bridged derivatives, such as formaldehyde-derived acetals, dithioacetals, or aminals. Formaldehyde acetals or formals are chemicals with many practical applications.…”

Section: Introductionmentioning

confidence: 99%

NHC-CDI Betaine Adducts and Their Cationic Derivatives as Catalyst Precursors for Dichloromethane Valorization

2021

View full text Add to dashboard Cite

Zwitterionic adducts of N-heterocyclic carbene and carbodiimide (NHC-CDI) are an emerging class of organic compounds with promising properties for applications in various fields. Herein, we report the use of the ICyCDI( p -Tol) betaine adduct ( 1a ) and its cationic derivatives 2a and 3a as catalyst precursors for the dichloromethane valorization via transformation into high added value products CH 2 Z 2 (Z = OR, SR or NR 2 ). This process implies selective chloride substitution of dichloromethane by a range of nucleophiles Na + Z – (preformed or generated in situ from HZ and an inorganic base) to yield formaldehyde-derived acetals, dithioacetals, or aminals with full selectivity. The reactions are conducted in a multigram-scale under very mild conditions, using dichloromethane both as a reagent and solvent, and very low catalyst loading (0.01 mol %). The CH 2 Z 2 derivatives were isolated in quantitative yields after filtration and evaporation, which facilitates recycling the dichloromethane excess. Mechanistic studies for the synthesis of methylal CH 2 (OMe) 2 rule out organocatalysis as being responsible for the CH 2 transfer, and a phase-transfer catalysis mechanism is proposed instead. Furthermore, we observed that 1a and 2a react with NaOMe to form unusual isoureate ethers, which are the actual phase-transfer catalysts, with a strong preference for sodium over other alkali metal nucleophiles.

show abstract

“…On the other hand, the development of functional transformations using the resulting methylene subunit from inert dihalomethane as a potentially useful C 1 module is particularly desirable and is of great significance . For representative examples, Uyeda and co-workers reported binuclear nickel and mononuclear cobalt complexes, which can promote cyclopropanation of alkenes in the presence of Zn powder as a reductant using CH 2 Cl 2 or CH 2 Br 2 as the methylene source. , However, no potential methylene intermediate species has been isolated and structurally characterized, which would be derived from CH 2 Cl 2 or CH 2 Br 2 activation.…”

Section: Introductionmentioning

confidence: 99%

Structure and Methylene Transfer Reactivity of Thiolate-Bridged Dichromium Methylene Complexes Derived from Dihalomethane via Cleavage of Two Carbon–Halogen Bonds

et al. 2021

View full text Add to dashboard Cite

Using sterically demanding Cp′ (Cp′ = η 5 -1,2,4-t Bu 3 C 5 H 2 ) as auxiliary ligands, coordinatively unsaturated thiolate-bridged Cr II Cr II complexes were obtained by a facile salt metathesis strategy. This dichromium system with vacant coordination sites can easily cleave the two carbon−halogen bonds of dihalomethane by a cooperative activation effect. Meanwhile, it can accommodate the resulting methylene moiety and two halide groups. Notably, an unprecedented thiolate-bridged Cr III Cr III methylene complex was successfully isolated and unambiguously characterized by X-ray crystallography. Unlike the common chemical inertness of the {Cr−CH 2 −Cr} subunit, this bridging methylene fragment not only can interact with CH 2 Br 2 to give ethylene but can also transfer to styrene to generate the corresponding cyclopropanated product. In addition, the Cr III Cr III complex containing two halides can be easily reduced by mild Zn powder to regenerate the initial Cr II Cr II complex. Furthermore, this [Cr 2 S 2 ] reaction scaffold can catalyze the cyclopropanation of styrenes using CH 2 Br 2 as the methylene source.

show abstract

The Application of Dichloromethane and Chloroform as Reagents in Organic Synthesis

Cited by 11 publications

References 139 publications

Cerebrosides and Steroids from the Edible Mushroom Meripilus giganteus with Antioxidant Potential

Cerebrosides and Steroids from the Edible Mushroom Meripilus giganteus with Antioxidant Potential

NHC-CDI Betaine Adducts and Their Cationic Derivatives as Catalyst Precursors for Dichloromethane Valorization

Structure and Methylene Transfer Reactivity of Thiolate-Bridged Dichromium Methylene Complexes Derived from Dihalomethane via Cleavage of Two Carbon–Halogen Bonds

Contact Info

Product

Resources

About