77765-22-1

Upstream product

• 25319-53-3 α,α,α-trideutero-ortho-xylene 
• 865-50-9 iodomethane-d3 
• 6630-33-7 ortho-bromobenzaldehyde 
• 19312-06-2 4,5-dihydro-4,4-dimethyl-2-phenoxazole 
• 34824-58-3 2-(2-bromophenyl)-1,3-dioxolan 
• 197714-94-6 4,4-Dimethyl-2-(2-trideuteriomethylphenyl)-4,5-dihydro-1,3-oxazole 

Downstream Products

• 167561-58-2 <1-(2-Trideuteriomethylcinnamoyl)prop-1-ylidene>triphenylphosphorane 
• 167561-44-6 Ethyl 2-trideuteriomethylcinnamoyl chloride 
• 105930-63-0 4-methyl-N'-(2-trideuteromethylbenzylidene)benzenesulfonohydrazide 

Relevant academic research and scientific papers

Sequential Hydrogen Tunneling in o-Tolylmethylene

o-Tolylmethylene 1 is a metastable triplet carbene that rearranges to o-xylylene 2 even at temperatures as low as 2.7 K via [1,4] H atom tunneling. Electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopical techniq

Diels-Alder Cycloaddition of C60 with Photochemically Generated Hydroxy to o-quinodimethanes Governed by Steric Factors: A Mechanistic Study

Photoexcited o-alkyl-substituted benzaldehydes add to C60through their photoenol reactive intermediates producing stable [4 + 2] fullerene adducts. A mechanistic approach for this reactivity of C60 is provided, based mainly on intra-

Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 10. Generation of 2-methylstyrylalkynes and their thermal cyclisation to 2-alkenylnaphthalenes

A series of nine 2-methylcinnamoyl phosphorus ylides 7 have been prepared and are found upon FVP at 500°C to undergo loss of Ph3PO to afford the corresponding styrylalkynes 8 whose fully assigned 13C NMR spectra are presented. FVP of the ylides at 900°C leads to cyclisation to give substituted naphthalenes 9-18; the mechanism of these reactions may proceed either by initial hydrogen atom loss or an initial [1,7]hydrogen shift, but an alternative route involving an initial [1,3]hydrogen shift has been ruled out by examination of a deuterium labelled analogue. For the α-phenyl ylides 7d and 7i a further cyclisation leads to benzo[c]fluorene derivatives and this process has been extended to a thiophene analogue to give fluoreno[3,4-b]thiophene. The formation of 2-ethylnaphthalene as the main product from the α-methoxycarbonyl ylide 7e is due to a secondary thermal reaction of methyl 2-naphthylacetate which may involve a radical chain reaction featuring, as the propagation step, an unusual homolytic substitution at a methoxy carbon by a 2-naphthylmethyl radical.

Novel Thermal Cyclisation of o-Methylstyrylalkynes to give 2-Alkenylnaphthalenes

Formation of o-methylstyrylalkynes by flash vacuum pyrolysis of the corresponding stabilised phosphorus ylides at 900 deg C is accompanied by unexpected cyclisation to give 2-alkenylnaphthalenes and deuterium labelling has been used to elucidate the mechanisms involved.

Rearrangements of the Isomeric Tolylmethylenes

We present evidence for a mechanism in which the isomeric tolylmethylenes interconvert via methylcycloheptatetraene intermediates.Photolysis (>470 nm) of diazo compounds 1-4, matrix isolated in argon at 10 K, generates triplet tolylmethylenes 8-11.Photoly

Direct Spectroscopic Observation of Intramolecular Hydrogen Shifts in Carbenes

Triplet o-tolylmethylene (13a) decays thermally to singlet o-xylylene (14a) in an argon matrix at temperatures as low as 4.6 K.The thermal, intramolecular -hydrogen shift has been observed directly by IR and UV spectroscopy.The carbene disappearance kinetics follow the standard (time)1/2 dependence, due to multiple reaction sites in the matrix.The small temperature dependence and non-Arrhenius behavior of the rate implicate a tunneling mechanism.In contrast, triplet 1-phenylethylidene (17a) is thermally stable in argon or xenon matrices at 10 K.Warming 17a to 65 K in a xenon matrix produces styrene (18a).The intramolecular -hydrogen shift has been observed directly by IR spectroscopy.The carbene disappearance kinetics show apparent first-order behavior.We estimate an upper limit of ca. 4.7 kcal/mol for the singlet-triplet energy gap in 17a.

Kinetics and Mechanism of Acid-Catalyzed Oxidation of Substituted Toluenes by Pyridinium Fluorochromate

The kinetics of oxidation of substituted toluenes by pyridinium fluorochromate(VI) (PFC), C5H5NCrO3F-, in aqueous acetic acid, in the presence of perchloric acid, have been studied.The main products are the corresponding aldehydes.While each of the oxidation is first order with respect to the oxidant, the rate is almost independent of the substrate concentration.The reactions depend on the first power of the concentration of acid.A kinetic isotope effect, kH/kD=5.4 at 30 deg C, was observed.Electron-releasing groups were found to moderately facilitate the reaction, whereas the electron-withdrawing groups were found to have a retardation effect.Correlation with ? value yielded a ρ value of -2.0.The reaction does not induce polymerization of acrylonitrile.The effects of temperature and solvent compositions were studied and activation parameters evaluated.These and related data suggest that the initial reaction involves hydrogen abstraction forming an intermediate which subsequently produces the corresponding aldehyde.