16954-38-4

Usage

Uses

Toluene-3,5-d2 (CAS# 16954-38-4) is a useful isotopically labeled research compound.

Upstream product

• 108-88-3 toluene 
• 1611-92-3 3,5-dibromotoluene 
• 16955-25-2 2,6-d₂-p-anisidine 

Downstream Products

• 2876-02-0 2,6-dideuterio-4-methylphenol 
• 115943-93-6 2-deuterio-4-methylphenol 
• 92891-99-1 [²H]-o-cresol 
• 37960-84-2 [3,5-D₂]benzoic acid 

Relevant academic research and scientific papers

Aqueous Oxidations Started by TiO2 Photoinduced Holes Can Be a Rate-Determining Step

In aqueous TiO2 photocatalytic hydroxylation of weakly polar aromatics, a series of inverse H/D KIEs of 0.7–0.8 were observed, which is different than the normal H/D kinetic isotope effects (KIEs) usually observed for polar aromatics. This result indicated that the oxidation started by photo-induced hvb + can be the rate-determining step.

Ruthenium dihydrogen complex for C-H activation: Catalytic H/D exchange under mild conditions

Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A p

H/D exchange at aromatic and heteroaromatic hydrocarbons using D 2O as the deuterium source and ruthenium dihydrogen complexes as the catalyst

Getting heavy: At temperatures as low as 50°C, D2O can serve as a cheap and readily available deuterium source for the efficient deuteration of aromatic and heteroaromatic substrates if nonclassical ruthenium hydride complexes are used as catalysts (see scheme). DFT calculations support a catalytic cycle comprising σ-bond metathesis as the key step for the exchange processes. (Chemical Equation Presented).

Room Temperature Activation of Aromatic C-H Bonds by Non-Classical Ruthenium Hydride Complexes Containing Carbene Ligands

Non-classical ruthenium hydride complexes are promising lead structures for the C-H bond activation and functionalization of aromatic compounds. In the present paper, the preparation and crystallographic characterisation of the first organo-metallic complexes bearing dihydrogen ligands and N-heterocyclic carbene ligands in the same coordination sphere are described. The mixed phosphine/ carbene complex [(IMes)Ru(H)2(H2) 2(PCy3)] (IMes = 1,3-dimesityl-1,3-dihydro-2H-imidazol-2- ylidene; 3a) shows a unique reactivity pattern in the inter- and intramolecular activation of C-H bonds. In particular, complex 3a effects a rapid and remarkably selective intermolecular activation of sp2 C-H bonds in simple aromatic compounds at room temperature.

DEUTERIUM ISOTOPE EFFECTS IN THE META PHOTOCYCLOADDITION OF AROMATIC COMPOUNDS TO ALKENES

Secondary deuterium isotope effects were observed in the meta photocycloaddition of several aromatic compounds to cyclopentene.

FRIEDEL-CRAFTS ALKYLATION OF ANISOLE AND ITS COMPARISON WITH TOLUENE. PREDOMINANT ORTHO-PARA SUBSTITUTION UNDER KINETIC CONDITIONS AND THE EFFECT OF THERMODYNAMIC ISOMERIZATIONS

The AlCl3 and BF3, as well as 65percent HPF6, catalyzed Friedel-Crafts alkylation of anisole with alkyl halides and alkohols was investigated.The alkylation of anisole with lower catalyst concentrations under mild conditions shows predominant ortho/para directing effect generally with a ratio of c.a. 2:1, with the amount of meta isomer uniformly less than 3percent.With "swamping" catalyst conditions the amount of meta substitution in methylation and ethylation can substantially increase.The isomer distribution in tert-butylation changes with time due to rapid ortho-para interconversion.Consequently, the AlCl3-catalyzed isomerization of isomeric alkylanisoles was also studied.In case of tert-butylanisoles, the ortho isomer shows relatively rapid conversion into para followed by much slower isomerization to meta.The para and meta isomers show isomerization to meta-para mixtures.Isomerization of ethyl-, isopropyl-, and benzylanisoles is generally slow whereas methylanisoles do not isomerize.Comparing results of the alkylation of anisole with toluene leads to the conclusion that the latter are readily affected by concurrent (and in some cases consecutive) isomerization.As the barrier for isomerization in the benzenium ion intermediates of the alkylations is higher in the case of CH3O- than CH3-substituted systems, anisole tends to give the kinetically controlled ortho-para alkylation products and the amount of meta isomer is low.Study of alkylation of 3,5-di- and 2,4,6-trideuterated toluene and anisole and comparing retained deuterium contents with isomer distributions shows that alkylated product formation in case of toluene, but not of anisole, is proceeded by intramolecular, 1,2-alkyl, and hydrogen-deuterium shifting resulting also in increased meta substitution.This effect is most predominant in methylation and ethylation where the alkyl shifts are intramolecular but not in tert-butylation and benzylation, where alkyl transfer is intermolecular.Isopropylation is intermediate in nature.No simple selectivity-reactivity relationship is indicated in the studied alkylation reactions.As shown in benzylations with increasingly electron-donating and -withdrawing substituted benzyl chlorides overall rate (i.e., substrate selectivity) and isomer distributions (i.e., regioselectivity) are not determined in the same step as significantly decreased substrate selectivity is not accompanied by loss of positional selectivity.Previously reported alkylations showing high degree of meta substitution therefore, must have been affected by thermodynamically controlled rearrangement processes, including intramolecular alkyl and hydrogen shifts in the arenium ion intermediates of the alkylation reactions.These are to be differentiated from possible subsequent product isomerizations.Under predominantly kinetic conditions anisole as well as toluene are substantially ortho-para directing in alkylations, as in other electrophilic aromatic substitutions.