43084-97-5

Upstream product

• 75-91-2 tert.-butylhydroperoxide 
• 100-07-2 4-methoxy-benzoyl chloride 
• 702-23-8 2-(4-Methoxyphenyl)ethanol 
• 110-05-4 di-tert-butyl peroxide 
• 123-11-5 4-methoxy-benzaldehyde 
• 105-13-5 4-Methoxybenzyl alcohol 
• 100-09-4 4-methoxybenzoic acid 

Downstream Products

• 19207-89-7 (methylthio)methyl 4-methoxybenzoate 
• 917241-31-7 (S)-cyclohept-2-en-1-yl 4-methoxybenzoate 
• 529-33-9 1,2,3,4-Tetrahydro-1-naphthol 
• 529-34-0 3,4-dihydronaphthalene-1(2H)-one 
• 68175-34-8 1-(tert-butyl)-4-(prop-1-en-1-yl)benzene 
• 56412-81-8 6-methoxy-3,4-diphenyl-1H-2-benzopyran-1-one 
• 1284251-41-7 4-methoxybenzoic acid [1,4]dioxan-2-yl ester 

Relevant academic research and scientific papers

Sunlight assisted solvent free synthesis of tert-butylperesters

A green and efficient methodology has been developed for the direct conversion of aryl aldehydes to the corresponding tert-butyl peresters. The reaction has been carried out in absence of any solvent and the sunlight is used as the green source of energy. In this reaction tetrabutylammonium iodide (TBAI) acts as the mild organo catalyst and tert-butyl hydroperoxide (TBHP) serve as the source of tert-butyl group.

A Woven Supramolecular Metal-Organic Framework Comprising a Ruthenium Bis(terpyridine) Complex and Cucurbit[8]uril: Enhanced Catalytic Activity toward Alcohol Oxidation

The self-assembly of a diamondoid woven supramolecular metal–organic framework wSMOF-1 has been achieved from intertwined [Ru(tpy)2]2+ (tpy=2,2′,6′,2′′-terpyridine) complex M1 and cucurbit[8]uril (CB[8]) in water, where the intermolecular dimers formed by the appended aromatic arms of M1 are encapsulated in CB[8]. wSMOF-1 exhibits ordered pore periodicity in both water and the solid state, as confirmed by a combination of 1H NMR spectroscopy, UV-vis absorption, isothermal titration calorimetry, dynamic light scattering, small angle X-ray scattering and selected area electron diffraction experiments. The woven framework has a pore aperture of 2.1 nm, which allows for the free access of both secondary and primary alcohols and tert-butyl hydroperoxide (TBHP). Compared with the control molecule [Ru(tpy)2]Cl2, the [Ru(tpy)2]2+ unit of wSMOF-1 exhibits a remarkably higher heterogeneous catalysis activity for the oxidation of alcohols by TBHP in n-hexane. For the oxidation of 1-phenylethan-1-ol, the yield of acetophenone was increased from 10 percent to 95 percent.

Bu4NI-catalyzed construction of tert-butyl peresters from alcohols

A new method for the synthesis of tert-butyl peresters directly from available alcohols catalyzed by Bu4NI at room temperature in an aqueous system was developed. Additionally, allylic esters could also be obtained by combing this method and Kharasch-Sosnovsky reaction via a two-step one-pot procedure.

Exploring the scope of pyridyl- and picolyl-functionalized 1,2,3-triazol-5-ylidenes in bidentate coordination to ruthenium(II) cymene chloride complexes

1-(2-Pyridyl)-, 4-(2-pyridyl)-, 1-(2-picolyl)-, and 4-(2-picolyl)- functionalized 1,3,4-trisubstituted 1,2,3-triazolium salts (1A-D, respectively) were investigated as N-heterocyclic carbene (trzNHC) precursors for bidentate coordination to ruthenium(II) through the CNHC and N pyridyl donors. In addition to the pyridyl and picolyl pendant groups, a variety of para-substituted phenyl rings were attached to the 1,2,3-triazolylidene via carbon or nitrogen atoms. The ruthenation was accomplished by metalation with Ag2O to form intermediate silver carbene complexes and subsequent transmetalation with [Ru(η6-p- cymene)Cl2]2. The cationic ruthenium complexes [Ru(η6-p-cymene)(trzNHC)Cl]+ (3A-C) were readily obtained with 1-(2-pyridyl)-, 4-(2-pyridyl)-, and 1-(2-picolyl)-1,2,3-triazolium salts (1A-C) but not with the 4-picolyl analogue (1D). The bidentate coordination of the ligand precursors 1 was followed by multinuclear NMR spectroscopy, revealing significant changes in chemical shifts for triazole C-5, pyridine nitrogen atoms, and the neighboring α-proton (H-6 pyridyl) in 13C, 15N, and 1H NMR spectra. The molecular composition of complexes 3A-C was confirmed by elemental analysis and positive ion electrospray ionization (ESI+) mass spectra, the latter showing ions corresponding to [Ru(η6-p-cymene)(trzNHC)Cl] +. The solid-state structures of the three representative complexes were confirmed by single-crystal X-ray analyses; all complexes displayed a typical piano-stool type configuration. Preliminary catalytic activity screening of 3A-C in the oxidation of selected primary and secondary alcohols with tert-butyl hydroperoxide (TBHP) to give carbonyl compounds is also discussed.

Synthesis of tert-butyl peresters from aldehydes by Bu4NI- catalyzed metal-free oxidation and its combination with the Kharasch-Sosnovsky reaction

A new tert-butyl peresters synthesis directly from aldehydes and TBHP was developed via Bu4NI-catalyzed aldehyde C-H oxidation. Mechanistic studies suggest that the protocol proceeds via a radical process. Combining the method with the Kharasch-Sosnovsky reaction offers a practical approach for the synthesis of allylic esters from simple aldehydes and alkenes via a two-step one-pot procedure.

Studies on enantioselective allylic oxidation of olefins using peresters catalyzed by Cu(I)-complexes of chiral pybox ligands

Enantioselective allylic oxidation of olefins with various peresters, using a catalytic amount of Cu(i)-pybox complex, can be tuned to achieve high asymmetric induction (up to 98% ee) by choosing a unique combination of a ligand and a perester at room temperature. The asymmetric induction in the reaction strongly depends on the nature of the substituents attached to the aryl ring of peresters. The presence of a gem-diphenyl group at C-5 and secondary or tertiary alkyl substituents at the chiral center (C-4) of the oxazoline rings is crucial for high enantioselectivity. A π-π stacking model has been proposed and discussed to explain the stereochemical outcome of the reaction. The Royal Society of Chemistry 2006.

Enantioselective allylic oxidation of cycloalkenes by using Cu(II)-tris(oxazoline) complex as a catalyst

Optically active copper(II)-tris(oxazoline) complex that was synthesized as a model compound of the active site of non-heme oxygenase, was found to catalyze allylic oxidation of cycloalkenes to give the corresponding 2-cycloalkenyl benzoates with moderate to excellent enantioselectivity (up to 93% ee) under die Kharash-Sosnovsky reaction conditions.

Spectroscopic and Kinetic Characteristics of Aroyloxyl Radicals. 1. The 4-Methoxybenzoyloxyl Radical

A detailed analysis of the time-resolved, UV-visible spectrum obtained by 308-nm laser flash photolysis of bis(4-methoxybenzoyl) peroxide proves that the broad, structureless absorption in the 500-800-nm region is due to the 4-methoxybenzoyloxyl radical.This radical also has an absorption at 320 nm.The long-wavelength absorption, for which there is less interference from other light-absorbing transients, has been used to measure absolute rate constants, k, for the reaction of 4-methoxybenzoyloxyl with a wide variety of organic substrates at ambient temperatures, e.g., cyclohexane, benzene, triethylsilane, cyclohexene, and 1,3-cyclohexadiene for which k in CCl4 = (5.3 +/- 3.0) x 105, (2.3 +/- ).2) x 106, (4.8 +/- 0.1) x 106, (6.4 +/- 0.3) x 107, and (4.8 +/- 0.2) x 108 M-1s-1, respectively.Compared with the tert-butoxyl radical the 4-methoxybenzoyloxyl radical is about as reactive in hydrogen atom abstractions but is very much more reactive in additions to multiple bonds.The rate constant for decarboxylation of 4-methoxybenzoyloxyl at 24 deg C is (3.4 +/- 0.1) x 105 s-1 in CCl4 but is reduced to 4 s-1 in CH3CN.The 4-methoxybenzoyloxyl radical can also be photodecarboxylated by using 700-nm light from a second laser or by using high power levels in the primary laser.

New Methods and Reagents in Organic Synthesis. 43. A New Synthesis of tert-Butyl Peroxycarboxylates Using Diethyl Phosphorocyanidate (DEPC)

Condensation of carboxylic acids with tert-butyl hydroperoxide has been smoothly achieved by the use of diethyl phosphorocyanidate and triethylamine under mild reaction conditions, giving tert-butyl peroxycarboxylates in good yields.Keywords - tert-butyl

REACTION OF NUCLEOPHILES WITH ELECTRON ACCEPTORS BY SN2 OR ELECTRON TRANSFER (ET) MECHANISMS: TERT-BUTYL PEROXYBENZOATE/DIMETHYL SULFIDE AND BENZOYL PEROXIDE/N,N-DIMETHYLANILINE SYSTEMS.

This study is one of a series that probes the reactions of nucleophiles with peroxides, reactions that can occur either by an initial S//N2 reaction or by an electron-transfer (ET) reaction. The products and kinetics are reported for the reaction of dimethyl sulfide and a series of ring-substituted aryl methyl sulfides with tert-butyl peroxybenzoate (TBP) and four ring-substituted TPB's. Kinetic analysis allows the separation of the rate constants for unimolecular homolysis (k//1) and those for the decomposition of the TBP by the sulfide (k//2). The bimolecular reaction is accelerated by electron-withdrawing substituents in the TBP; for example, when 3,5-(NO//2)//2-TBP is used, k//2/k//1 is 12,000. The products that are formed are consistent with a radical process; however, this evidence is not regarded as conclusive.