33206-31-4

Upstream product

• 82700-23-0 tert-Butyl-dimethyl-(3-methyl-3,8a-dihydro-benzo[c][1,2]dioxin-3-yloxy)-silane 
• 1745-81-9 o-Allylphenol 
• 1746-13-0 allyl phenyl ether 
• 762-72-1 allyl-trimethyl-silane 
• 7035-11-2 4-chloro-2-chloromethyl-1-methoxy-benzene 
• 103-79-7 1-phenyl-acetone 
• 201738-82-1 (Z)-1-phenyl-2-tert-butyldimethylsiloxy-1-propene 
• 90-01-7 salicylic alcohol 
• 110-82-7 cyclohexane 
• 82466-11-3 2-methyl-4H-benzo[d][1,3]dioxine 

Downstream Products

• 1746-11-8 2-methyl-2,3-dihydro-1-benzofuran 

Relevant academic research and scientific papers

Boron insertion into alkyl ether bonds via zinc/nickel tandem catalysis

Mild methods to cleave the carbon-oxygen (C?O) bond in alkyl ethers could simplify chemical syntheses through the elaboration of these robust, readily available precursors. Here we report that dibromoboranes react with alkyl ethers in the presence of a nickel catalyst and zinc reductant to insert boron into the C?O bond. Subsequent reactivity can effect oxygen-to-nitrogen substitution or one-carbon homologation of cyclic ethers and more broadly streamline preparation of bioactive compounds. Mechanistic studies reveal a cleavage-then-rebound pathway via zinc/nickel tandem catalysis.

Methoxy-substituted α, n-didehydrotoluenes. photochemical generation and polar vs diradical reactivity

The photoreactivity of differently substituted (chloromethoxybenzyl)trimethylsilanes in alcohols and alcohol/water mixtures has been investigated by means of a combined computational and experimental approach. Subsequent elimination of the chloride anion and the trimethylsilyl cation gives the corresponding methoxy-substituted α,n-didehydrotoluenes (α,n-MeO-DHTs). The rate of desilylation is evaluated through the competition with arylation via phenyl cation (ca. 108s-1). α,2-MeO- and α,4-MeO-DHTs show a purely radical behavior (H abstraction from the solvent, methanol), while α,3-MeO-DHT shows mainly a ionic chemistry, as when the parent α,3-DHT is thermally generated. This is likely due to triplet-singlet surfaces crossing occurring during desilylation.

Novel photohydration of non-conjugated aryl/olefin bichromophores within cyclodextrin cavities

Cyclodextrin media are used to achieve photochemical water addition to isolated, acyclic double bonds via intramolecular interaction with excited arenes.

Azophenyl compounds

Azophenyl compounds of the formula: STR1 wherein R1 is an o-, p-directing substituent; R2 is a substituted or unsubstituted β-hydroxyalkyl group; R3 is an aromatic carbocyclic or heterocyclic group which is mono- or poly-cyclic and is substituted or unsubstituted; and wherein the benzene ring A may contain one or more further substituents. The compounds are useful as dyestuffs (if they are themselves colored) or as intermediates in the preparation of dyestuffs.

New homologation of 2-hydroxy and 2-mercapto benzylic alcohols

The reaction of benzo-1,3-dioxanes or benzo-1,3-oxathianes 1 [easily prepared from 2-hydroxy or 2-mercapto benzylic alcohols (3 or 4, respectively) and carbonyl compounds] with an excess of lithium and a catalytic amount of DTBB (4.5 mol %) in THF at room temperature or -78°C leads, alter hydrolysis with water, to the corresponding homobenzylic alcohols 2. Cyclisation of compounds 2 under acidic (85% H3PO4) or neutral (Ph3P/DIAD) conditions affords the expected heterocycles 5.

Acid-catalyzed hydrolysis of some primary alkyl phenyl ethers

Products were analyzed and rate constants of disappearance and hydrolysis, alkylation and/or rearrangement were measured for methyl, ethyl, propyl and allyl phenyl ethers by GC in concentrated aqueous perchloric acid solutions. Chlorination of the substrate and possibly of the product, phenol, was observed beside the hydrolysis of methyl phenyl ether and a slight chlorination of phenol beside the hydrolysis of ethyl phenyl ether. A marked Claisen rearrangement to isopropylphenols and alkylation to propyl isopropylphenyl ethers were observed in addition to the hydrolysis of propyl phenyl ether. The Claisen rearrangement to o-allylphenol was estimated to be quantitative in the case of allyl phenyl ether. The change of the reaction mechanism from A-2 (MeOPh and EtOPh) possibly via A-2(carbocation)(PrOPh?) to A-1 (allyl phenyl ether and possibly PrOPh) was deduced from the products, reaction rates, activation parameters, solvent deuterium isotope effect and parameters of excess acidity plots. Acta Chemica Scandinavica 1997.

Reactions of allyl phenyl ether in high-temperature water with conventional and microwave heating

In a systematic study, allyl phenyl ether (1) was heated in water for 1 h at temperatures of 180°C and above. Parallel experiments were conducted with a conventionally heated autoclave and a recently developed microwave batch reactor. Relatively modest temperature differences resulted in diverse product distributions, and these were independent of the method of heating. Maximum conversion of 1 to 2-allylphenol occurred at 200°C (56%) and to 2-methyl-2,3-dihydrobenzofuran at 250°C (72%). Although 2-(2-hydroxyprop-1-yl)phenol comprised less than 1% of the product mixture at both 180 and 260°C, it accounted for 37% at 230°C. The reaction sequence was investigated by heating intermediates individually at selected temperatures up to 290°C. Hydration of 2-allylphenol to 2-(2-hydroxyprop-1-yl)phenol was partially reversible. The work showed that high-temperature water constitutes an environmentally benign alternative to the use of acid catalysts or organic solvents and offers scope for interconversion of alcohols and alkenes.

Photochemistry of o-Allylphenol. Identification of the Minor Products and New Mechanistic Proposals

The photochemistry of o-allylphenol (1) in cyclohexane has been reinvetigated.Besides the previously reported cyclic ethers 2 and 3, seven additional minor photoproducts have been detected.Spectroscopic methods, coupled with independent synthesis, have allowed their identification as 2-methylbenzofuran (5), o-propylphenol (8), the epoxide 4, the dihydroxy compound 9, the cyclohexyl ether 6, o-(cyclohexylmethyl)phenol (10), and the dimer 7.Their formation is rationalized through new mechanistic pathways, which involve initial intermolecular electron and/or proton transfer between two molecules of o-allylphenol, as well as di-?-methane rearrangement.Key intermediates appear to be radical V, carbenium ion IX, and carbene XI.This is supported by photolysis of o-allylphenyl acetate (11), which leads to the formation of a radical pair, followed by in cage recombination to the photo-Fries products 12 and 13 or, alternatively, diffusion of the radicals out of the solvent cage to afford the minor products 2, 5, and 6, identical to those obtained by photolysis of 1.

REGIOSPECIFIC ORTHO OXYFUNCTIONALIZATION OF SUBSTITUTED BENZENES WITH SINGLET OXYGEN

A new procedure for regiospecific ortho oxyfunctionalization of phenylacetones, phenylacetic acid esters and phenylacetaldehyde has been developed.The method involves tert-butyldimethylsilylation, singlet oxygenation and successive reduction.