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.
PRODUCTION METHOD OF DICHLOROADAMANTANE
-
Paragraph 0030; 0033, (2018/09/02)
PROBLEM TO BE SOLVED: To provide a production method suitable for industrial production of dichloroadamantanes. SOLUTION: A method for producing dichloroadamantanes represented by formula (2) is provided, in which adamantanes represented by formula (1) are mixed with thionyl chloride by 4 to 10 times moles to 1 mole of the adamantanes in the presence of sulfuric acid to react. In formula (1), R1 to R3 each independently represent H, a halogen atom, an alkyl group or an aryl group, and when R1 to R3 represent Cl, the number of Cl is at most 1, and when no Cl is included, at least one of R1 to R3 is H. In formula (2), one of R4 to R6 is a chlorine atom. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
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.
