108733-06-8

Upstream product

• 13389-70-3 bis(4-methylphenyl)methyl chloride 
• 762-72-1 allyl-trimethyl-silane 
• 4957-14-6 4,4'-dimethyldiphenylmethane 
• 58493-75-7 bis(4-methyldiphenyl)methylium 

Relevant academic research and scientific papers

Oxidative generation of diarylcarbenium ion pools

(Figure Presented) "Cation pools" of diarylcarbenium ions have been generated by the oxidative C-H bond dissociation of diarylmethanes using anodic oxidation. "Diarylcarbenium ion pools" thus generated react with various nucleophiles, such as allylsilanes

Generation of diarylcarbenium ion poolsviaelectrochemical C-H bond dissociation

The "cation pools" of diarylcarbenium ions have been generated by the low-temperature electrochemical oxidation of diphenylmethane derivatives. In addition to diphenylmethanes having various substituents, 9,10-dihydroanthracene, dibenzosuberane, and xanth

Relative Reactivities of Alkyl Chlorides under Friedel-Crafts Conditions

Competition experiments have been performed to determine the relative reactivities of 23 alkyl chlorides toward allyltrimethylsilane in the presence of catalytic amounts of ZnCl2.The krel scale spans over 11 orders of magnitude from 1-adamantyl chloride (least reactive) to bis(p-methoxyphenyl)methyl chloride (most reactive compound).A fair correlation between the alkylating ability and the SN1 reactivity in solvolysis reactions is found, thus providing a quantitative basis for our long-standing working hypothesis that Lewis acid-catalyzed additions of alkyl halides to CC multiple bonds only yield 1:1 products if the reactants ionize faster than the products.Trityl chlorides do not follow this correlation and are 1E5 times less reactive than predicted from their SN1 reactivities. - Key Words: Alkylation / Allylation / Carbenium ions / Friedel-Crafts reactions / Linear free energy relationships

Kinetics of the reactions of allylsilanes, allylgermanes, and allylstannanes with carbenium ions

Second-order rate constants for the reactions of para-substituted diarylcarbenium ions (ArAr'CH+ = 1) with allylsilanes 2, allylgermanes 3, and allylstannanes 4 have been determined in CH2Cl2 solution at -70 to -30°C. Generally, the attack of ArAr'CH+ at the CC double bond of the allylelement compounds 2-4 is rate-determining and leads to the formation of the β-element-stabilized carbenium ions 5, which subsequently react with the negative counterions to give the substitution products 6 or the addition products 7. For compounds H2C = CHCH2MPh3, the relative reactivities are 1 (M = Si), 5,6 (M = Ge), and 1600 (M = Sn). From the relative reactivities of compounds H2C=CHCH2X (X = H, SiBu3, SnBu3), the activating effect of an allylic trialkylsilyl (5 × 105) and trialkylstannyl group (3 × 109) is derived. This effect is strongly reduced, when the alkyl groups at Si or Sn are replaced by inductively withdrawing substituents, and an allylic SiCl3 group deactivates by a factor of 300 (comparison isobutene/2k). A close analogy between the reactions of alkenes and allylelement compounds with carbenium ions is manifested, and the different reaction series are connected by well-behaved linear free energy relationships. The relative reactivities of terminal alkenes and allylelement compounds are almost independent of the electrophilicities of the reference carbenium ions (constant selectivity relationship), thus allowing the construction of a general nucleophilicity scale for these compounds.

ELECTROPHILIC ATTACK AT ALLYLSILANES: A QUANTITATIVE DETERMINATION OF THE β-SILYL EFFECT

The relative reactivities of allylsilanes and alkenes towards diarylmethyl cations have been determined by competition experiments.Introduction of a β-trimethylsilyl group increases the reactivity of propene towards the diphenylmethyl cation by a factor o