62115-71-3Relevant articles and documents
Methylation with Dimethyl Carbonate/Dimethyl Sulfide Mixtures: An Integrated Process without Addition of Acid/Base and Formation of Residual Salts
Chan, Bun,Lui, Matthew Y.,Lui, Yuen Wai
, (2022/01/08)
Dimethyl sulfide, a major byproduct of the Kraft pulping process, was used as an inexpensive and sustainable catalyst/co-reagent (methyl donor) for various methylations with dimethyl carbonate (as both reagent and solvent), which afforded excellent yields of O-methylated phenols and benzoic acids, and mono-C-methylated arylacetonitriles. Furthermore, these products could be isolated using a remarkably straightforward workup and purification procedure, realized by dimethyl sulfide‘s neutral and distillable nature and the absence of residual salts. The likely mechanisms of these methylations were elucidated using experimental and theoretical methods, which revealed that the key step involves the generation of a highly reactive trimethylsulfonium methylcarbonate intermediate. The phenol methylation process represents a rare example of a Williamson-type reaction that occurs without the addition of a Br?nsted base.
Nickel/Cobalt-Catalyzed Reductive Hydrocyanation of Alkynes with Formamide as the Cyano Source, Dehydrant, Reductant, and Solvent
Zhang, Jin,Luo, Cui-Ping,Yang, Luo
supporting information, p. 283 - 288 (2020/12/01)
A Ni/Co co-catalyzed reductive hydrocyanation of various alkynes was developed for the production of saturated nitriles. Hydrocyanic acid is generated in situ from safe and readily available formamide. Formamide played multiple roles as a cyano source, dehydrant, and reductant for the NiII pre-catalyst and vinyl nitriles, along with acting as the co-solvent in this reaction. Detailed mechanistic investigation supported a pathway via hydrocyanation of C≡C bond and the subsequent reduction of C=C bond. Wide substrate scope, the employment of a cheap and stable nickel salt as pre-catalyst, a safe cyano source and convenient experimental operation render this hydrocyanation practical for the laboratory synthesis of saturated nitriles. (Figure presented.).
Preparation method of nitrile compounds with formamide as cyanide source
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Paragraph 0015-0023; 0089-0090, (2020/03/09)
The invention discloses a preparation method of nitrile compounds. According to the preparation method, formamide used as a cyanide source undergoes a hydrocyanation reaction with various types of olefins under the action of a nickel catalyst to generate various nitrile compounds, wherein a reaction temperature is 60-160 DEG C and reaction time is 6-36 hours. The method overcomes the defects thata traditional olefin hydrocyanation reaction is complex in operation, needs to use a highly toxic cyanide source as a reaction raw material and the like. According to the method, simple, cheap, greenand non-toxic formamide is used as a cyano source, other dehydrating agents (such as phosphorus pentoxide and phosphorus oxychloride) do not need to be added, and cyano anions are generated through spontaneous dehydration of formamide under the catalysis of Lewis acid and undergo a hydrocyanation reaction with olefin in situ to generate nitrile compounds; reaction conditions are simple, operationis easy, and economical performance and high efficiency are realized; meanwhile, the method is applicable to various monosubstituted and disubstituted aliphatic and aromatic olefins, and shows good substrate universality; the nitrile compounds are insensitive to air, moisture and light and high in yield; and the preparation method is simple in product separation and purification and has good application prospects.
