134310-99-9

Upstream product

• 7525-21-5 4-methoxy-4'-methylbenzhydryl chloride 
• 76-63-1 allytriphenyltin 
• 762-72-1 allyl-trimethyl-silane 
• 429677-37-2 (p-methoxyphenyl)(p-tolyl)methylium cation 
• 18146-00-4 allyloxytrimethylsilane 
• 104-87-0 4-methyl-benzaldehyde 
• 100-66-3 methoxybenzene 
• 24850-33-7 allyltributylstanane 
• 22865-60-7 1-(4-methoxybenzyl)-4-methylbenzene 

Downstream Products

• 1628714-17-9 (E)-1-methoxy-4-(1-p-tolylbut-2-enyl)benzene 
• 1628714-18-0 (Z)-1-methoxy-4-(1-p-tolylbut-2-enyl)benzene 

Relevant academic research and scientific papers

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

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

A convenient method for the synthesis of 4,4-diarylbut-1-enes via the successive allylation of aromatic aldehydes and the Friedel-Crafts alkylation reaction of aromatic nucleophiles with the intermediary benzyl silyl ethers using HfCl4 or Cl2Si(OTf)2

The three-component coupling reaction among aromatic aldehydes, allyltrimethylsilane and aromatic nucleophiles is efficiently performed by the promotion of HfCl4. A similar reaction occurs using allyltributyltin as the first nucleophile to aromatic aldehydes with a catalytic amount of Cl2Si(OTf)2 generated in situ from SiCl4 and AgOTf.

Gemeinsame Ursache enthalpischer und entropischer Substituenteneffekte bei Reaktionen von Benzhydryl-Kationen mit Nucleophilen

Stichworte: Carbokationen * Lineare Freie-Enthalpie-Beziehung * Reaktionsmechanismen * Substituenteneffekte

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.