Microwave assisted solid additive effects in simple dry chlorination reactions with n-chlorosuccinimide

Bucoş, Madalina; Villalonga-Barber, Carolina; Micha-Screttas, Maria; Steele, Barry R.; Screttas, Constantinos G.; Heropoulos, Georgios A.

doi:10.1016/j.tet.2010.01.033

Cited by 11 publications

(5 citation statements)

References 41 publications

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“…In continuation of our previous studies on C–H bond halogenations, we herein report a safe, cheap, atom-economic, air- and moisture-tolerating approach for the side-chain chlorination of a range of arenes and alkanes with yields (of isolated product) of up to 85% at 25–30 °C with N -hydroxyphthalimide 1 (NHPI) as radical initiator. …”

Section: Introductionmentioning

confidence: 94%

Mild Aliphatic and Benzylic Hydrocarbon C–H Bond Chlorination Using Trichloroisocyanuric Acid

et al. 2017

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We present the controlled monochlorination of aliphatic and benzylic hydrocarbons with only 1 equiv of substrate at 25-30 °C using N-hydroxyphthalimide (NHPI) as radical initiator and commercially available trichloroisocyanuric acid (TCCA) as the chlorine source. Catalytic amounts of CBr reduced the reaction times considerably due to the formation of chain-carrying ·CBr radicals. Benzylic C-H chlorination affords moderate to good yields for arenes carrying electron-withdrawing (50-85%) or weakly electron-donating groups (31-73%); cyclic aliphatic substrates provide low yields (24-38%). The products could be synthesized on a gram scale followed by simple purification via distillation. We report the first direct side-chain chlorination of 3-methylbenzoate affording methyl 3-(chloromethyl)benzoate, which is an important building block for the synthesis of vasodilator taprostene.

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Section: Introductionmentioning

confidence: 94%

Mild Aliphatic and Benzylic Hydrocarbon C–H Bond Chlorination Using Trichloroisocyanuric Acid

et al. 2017

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“…Generally, in the chlorination reaction involving the use of NCS, chlorination can proceed either through Cl • or Cl + or Cl 2 . 24,27,30,36 However, in the present method there is no involvement of free radical since use of a free radical initiator and inhibitor showed no effect on reaction rate. In our experimental study, the attacking species may be Cl + when NCS was used as a chlorinating agent in the presence of acid and absence of NaCl using water as a solvent (Table 1).…”

Section: ■ Results and Discussionmentioning

confidence: 76%

“…), 26,27,29 and use of microwave conditions which are not suitable for large scale processes. 30 The present system overcomes all these disadvantages of recently reported systems and has the advantages of higher yields, higher selectivities, and elimination of catalyst and organic solvent and is easy to scale-up under mild reaction conditions.…”

Section: ■ Introductionmentioning

confidence: 84%

“…The use of p -TsOH , and NCS , is reported in literature for chlorination; however, the disadvantages of these methods involve the use of organic solvents , which have serious environmental impacts, poor yield and selectivities, solvent-free conditions operating at high temperature (up to 80 °C) and in long durations, use of expensive catalyst (gold, etc. ), ,, and use of microwave conditions which are not suitable for large scale processes . The present system overcomes all these disadvantages of recently reported systems and has the advantages of higher yields, higher selectivities, and elimination of catalyst and organic solvent and is easy to scale-up under mild reaction conditions.…”

Section: Introductionmentioning

confidence: 86%

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Efficient and Facile Chlorination of Industrially-Important Aromatic Compounds using NaCl/p-TsOH/NCS in Aqueous Media

Mahajan

Kumar

Dwivedi

et al. 2012

Ind. Eng. Chem. Res.

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A simple and efficient process for the chlorination of industrially important aromatic compounds using NaCl/p-TsOH/NCS in aqueous media under mild conditions is described. The addition of NaCl increases the yield of chlorinated product and decreases the reaction time in the presence of p-toluenesulphonic acid (p-TsOH) and N-chlorosuccinimide (NCS). The present method furnishes higher selectivities and yields of chlorinated products under mild reaction conditions in a short reaction time. Organic solvent-free conditions, a feature of green chemistry, was successively used not only for the reactions but also for the isolation of products at the end of the reaction, which seems to be the most promising methodology from the viewpoint of a green approach to organic synthesis.

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“…N -halosuccinimides are very popular as halogen-transfer reagents [ 5 , 6 , 7 , 8 , 9 ]; however they are usually not reactive enough for direct halogenation and require a Lewis acid or a Brønsted acid catalyst. The catalysts employed are usually moisture sensitive, they are often metallic or strongly acidic, produce toxic waste, and are costly.…”

Section: Introductionmentioning

confidence: 99%

Brønsted Acidic Ionic Liquid Accelerated Halogenation of Organic Compounds with N-Halosuccinimides (NXS)

Lü

You

et al. 2012

Molecules

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The Brønsted-acidic ionic liquid 1-methyl-3-(4-sulfobutyl)imidazolium triflate [BMIM(SO3H)][OTf] was demonstrated to act efficiently as solvent and catalyst for the halogenation of activated organic compounds with N-halosuccinimides (NXS) under mild conditions with short reaction times. Methyl aryl ketones were converted into α-halo and α,α-dihaloketones, depending on the quantity of NXS used. Ketones with activated aromatic rings were selectively halogenated, however in some cases mixtures of α-halogenated ketone and ring-halogenated ketones were obtained. Activated aromatics were regioselectively ring halogenated to give mono- and dihalo-substituted products. The [BMIM(SO3H)][OTf] ionic liquid (IL-A) was successfully reused eight times in a representative monohalogenation reaction with no noticeable decrease in efficiency. An effective halogenation scale-up in this IL is also presented. The reactivity trend and the observed chemo- and regioselectiivities point to an ET process in these IL-promoted halofunctionalization reactions.

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Microwave assisted solid additive effects in simple dry chlorination reactions with n-chlorosuccinimide

Cited by 11 publications

References 41 publications

Mild Aliphatic and Benzylic Hydrocarbon C–H Bond Chlorination Using Trichloroisocyanuric Acid

Mild Aliphatic and Benzylic Hydrocarbon C–H Bond Chlorination Using Trichloroisocyanuric Acid

Efficient and Facile Chlorination of Industrially-Important Aromatic Compounds using NaCl/p-TsOH/NCS in Aqueous Media

Brønsted Acidic Ionic Liquid Accelerated Halogenation of Organic Compounds with N-Halosuccinimides (NXS)

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