16104-50-0Relevant articles and documents
Tolstikov et al.
, p. 3191 (1972)
Lerman et al.
, (1971)
KOtBu as a single electron donor? Revisiting the halogenation of alkanes with CBr4 and CCl4
Emery, Katie J.,Young, Allan,Arokianathar, J. Norman,Tuttle, Tell,Murphy, John A.
supporting information, (2018/05/22)
The search for reactions where KOtBu and other tert-alkoxides might behave as single electron donors led us to explore their reactions with tetrahalomethanes, CX4, in the presence of adamantane. We recently reported the halogenation of adamantane under these conditions. These reactions appeared to mirror the analogous known reaction of NaOH with CBr4 under phase-transfer conditions, where initiation features single electron transfer from a hydroxide ion to CBr4. We now report evidence from experimental and computational studies that KOtBu and other alkoxide reagents do not go through an analogous electron transfer. Rather, the alkoxides form hypohalites upon reacting with CBr4 or CCl4, and homolytic decomposition of appropriate hypohalites initiates the halogenation of adamantane.
METHOD FOR PRODUCING CHLOROADAMANTANES
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Paragraph 0031; 0032, (2018/09/08)
PROBLEM TO BE SOLVED: To provide a production method suitable for industrial production of chloroadamantanes. SOLUTION: There is provided a method for producing chloroadamantanes represented by formula (2), in which bridgehead positions (1-, 3-, 5-, and 7-positions) of the adamantane are chlorinated, by mixing and reacting adamantanes (1) with thionyl chloride in the presence of sulfuric acid. (R1 to R3 each independently represent H or Ry; Ry represents a halogen atom, an alkyl group, or an aryl group; when there are a plurality of Ry's, respective Ry may be the same or different.) (When substituents R1, R2 and/or R3 are Ry's in the formula (1), substituents R4 to R6 at positions corresponding to the substituents R1 to R3 are the same as the substituents R1 to R3.) SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
Cross-coupling of non-activated chloroalkanes with aryl grignard reagents in the presence of iron/N-heterocyclic carbene catalysts
Ghorai, Sujit K.,Jin, Masayoshi,Hatakeyama, Takuji,Nakamura, Masaharu
experimental part, p. 1066 - 1069 (2012/04/10)
An efficient and high-yielding cross-coupling reaction of various primary, secondary, and tertiary alkyl chlorides with aryl Grignard reagents was achieved by using catalytic amounts of N-heterocyclic carbene ligands and iron salts. This reaction is a simple and efficient arylation method having applicability to a wide range of industrially abundant chloroalkanes, including polychloroalkanes, which are challenging substrates under conventional cross-coupling conditions.