22583-66-0

Usage

InChI:InChI=1/C15H22O/c1-14(2,3)12-9-7-11(8-10-12)13(16)15(4,5)6/h7-10H,1-6H3

Upstream product

• 630-18-2 tert-butyl isocyanide 
• 63488-10-8 4-tert-butylmagnesium bromide 
• 1012-72-2 1,4-di-tert-butylbenzene 
• 201230-82-2 carbon monoxide 
• 3972-65-4 1-bromo-4-tert-butylbenzene 
• 3282-30-2 pivaloyl chloride 
• 507-20-0 tertiary butyl chloride 
• 1710-98-1 p-tert-butyl benzoyl chloride 
• 677-22-5 tert-butylmagnesium chloride 
• 938-16-9 2,2-dimethylpropiophenone 
• 89379-02-2 tert-butylmercury iodide 
• 71-43-2 benzene 
• 594-19-4 tert.-butyl lithium 
• 253185-03-4 tert-butylbenzene 

Downstream Products

• 34235-16-0 1-(4-tert-Butylphenyl)-2,2-dimethyl-1-propanol 
• 19839-00-0 4-tert-Butylpivalophenonazin 
• 939-97-9 4-tert-Butylbenzaldehyde 
• 26110-91-8 1-tert-Butyl-4-(2,2-dimethylpropyl)benzol 
• 86439-91-0 Bis<1-(4-tert-butylphenyl)-2,2-dimethylpropyl>diazen 
• 107557-71-1 Bis<1-chlor-1-(4-tert-butylphenyl)-2,2-dimethylpropyl>diazen 
• 345948-38-1 meso-3,4-Bis(4-tert-butylphenyl)-2,2,5,5-tetramethylhexan 
• 86439-83-0 DL-3,4-Bis(4-tert-butylphenyl)-2,2,5,5-tetramethylhexan 
• 86696-32-4 p-t-butyl-α-t-butylbenzyl chloride 
• 120136-19-8 3-Nitro-benzenesulfonic acid 1-(4-tert-butyl-phenyl)-2,2-dimethyl-propyl ester 
• 120135-99-1 Toluene-4-sulfonic acid 1-(4-tert-butyl-phenyl)-2,2-dimethyl-propyl ester 

Relevant academic research and scientific papers

Rhodium-Catalyzed and Chiral Zinc Carboxylate-Assisted Allenylation of Benzamides via Kinetic Resolution

Enantioenriched allenes are important building blocks. While they have been accessed by other coupling methodologies, enantioenriched allenes have been rarely obtained via C-H activation. In this work, kinetic resolution of tertiary propargyl alcohols as an allenylating reagent has been realized via rhodium(III)-catalyzed C-H allenylation of benzamides. The reaction proceeded efficiently under mild conditions, and both the allenylated products and the propargyl alcohols were obtained in high enantioselectivities with an s-factor of up to 139. The resolution results from bias of the two propargylic substituents and is assisted by a chiral zinc carboxylate additive.

Chiral phosphoric acid catalyzed asymmetric transfer hydrogenation of bulky aryl ketones with ammonia borane

An asymmetric transfer hydrogenation of bulky aryl ketones with ammonia borane was successfully realized with chiral phosphoric acid (CPA) as catalyst and water as additive. A variety of optically active secondary alcohols were obtained in good to high yi

Cp?Co(III)-Catalyzed C-H Alkylation with Maleimides Using Weakly Coordinating Carbonyl Directing Groups

A novel protocol for ortho-C-H alkylation of aromatic and heteroaromatic ketones and esters under Cp?Co(III) catalysis has been developed for the first time. The reaction proceeds through initial cyclometalation via weak chelation-assisted C-H bond activation, followed by coordination of activated alkene, insertion between Co-C, and protodemetalation.

Homolytic base-promoted aromatic alkylations by alkylmercury halides

Electron transfer chain reactions leading to substitution in electronegatively substituted benzene derivatives can be observed with alkylmercury halides in the presence of proton accepters such as DABCO. Promotion by base involves the abstraction of a proton from the substituted cyclohexadienyl adduct radical to form a radical anion which readily transfers an electron to RHgX with the regeneration of R.. Aromatic substitutions involving t-Bu. are highly regioselective and yield products of only para attack for PhCHO, PhCOCH3, PhCOCMe3, PhCOPh, PhCN, phthalimides, or 1,2-dicyanobenzene. The ortho/para substitution products are observed for isophthaldehyde or 1,3-dicyanobenzene, while 1,4-dicyanobenzene yields the ortho substitution product. At 25-35°C substitution by t-Bu. ortho to an ester group is not observed and m- or p-cyanobenzoate esters yield only products of substitution ortho to the cyano group. With the isopropyl radical substitution ortho to the ester function is observed with diethyl isophthalate. Intramolecular radical cyclizations of the radical adducts of 1-aryl-4-penten-1-ones leading to α-tetralones is also promoted by the presence of DABCO. When the aryl group contains a para ester function, spirocyclizatien occurs leading to a rearrangement acyl radical which can be oxidized by t-BuHgCl to the acyl cation and the carboxylic acid.

The photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction (Part 4): methanol-olefins, methyl 4-cyanobenzoate

Dicyanobenzene-1,4 (1) and -1,2 are known to undergo substitution upon irradiation, in the presence of an olefin, in acetonitrile-methanol (3:1) solution.The products are 1:1:1 (methanol:olefin:aromatic) adducts, substituted on the aromatic ring with loss of a cyano group.This reaction, referred to as the photo-NOCAS (nucleophile-olefin combination, aromatic substitution) reaction, has been shown to be fairly general with regard to the olefin and the nucleophile that can be incorporated.Less is known about the scope of the reaction incorporating other electron-withdrawing substituted aromatic molecules.The purpose of this study was to determine if methyl 4-cyanobenzoate (10) would also take part in this reaction, to form 4-substituted aromatic esters.Irradiation of acetonitrile-methanol solutions of 10 and olefins 2,3-dimethyl-2-butene (2) and 1-methylcyclohexene (5) gave cyclic imine esters, 11 and 13, respectively, instead of photo-NOCAS products.The photo-NOCAS products were obtained when the codonor biphenyl (4) was added to the irradiation mixture.Formation of the cyclic imine ester is attributed to excitation of the charge-transfer complex formed between 10 and the olefin.The addition of biphenyl (4) serves to generate the contact radical ion pair (CRIP) upon irradiation of the charge-transfer complex between 10 and 4.This CRIP can dissociate to the solvent-separated radical ions, the radical cation of 4 can accept an electron from the olefin, and the olefin radical cation can go on to give the photo-NOCAS products.Irradiation of a solution of 10 and 2 in nonpolar solvent (benzene) gave the oxetane, believed to arise from the exciplex.In addition to photo-NOCAS products from 10, 4-cyanophenylketones 17 and 23 are also formed by attack of the β-alkoxyalkyl radical at the carboxyl carbonyl.The differences in behaviour between 1,4-dicyanobenzene (1) and methyl 4-cyanobenzoate (10) under these reaction conditions are described and explained.

Application of Force Field Calculations, 7. - Synthesis and Thermolysis of 1,1'-Disubstitueted trans-Azoneopentanes. - Steric and Resonance Effects of the Substituents on the Thermal Stability of Secondary Azoalkanes

A number of secondary azoalkanes 1, R1R2CH-N=N-CHR1R2, R1 = t-C4H9, R2 = aryl (meso- and D,L-1a-i) and R2 = cyclo-C6H11 (D,L-1k), have been synthesized by partial catalytic hydrogenation of the corresponding ketazines.The configuration of 1 was elucidated by photolysis of crystalline samples of 1, which yielded the dimers 6 with retention of configuration.The kinetics of thermal fragmentation of 1a-k and of 1n (R1 = CH3, R2 = C6H5) into the radicals 7 was followed by DSC.The activation parameters were determined by fitting theoretical curves to the experimental data with the help of a computer program. - The rate of decomposition of 1 with R1, R2 = alkyl is sterically accelarated by increasing size of the substituents (back strain), but the fragmentation of 1a-i (R2 = aryl) is sterically inhibited, e.g. k 2 = C6H5, R1 = t-C4H9)>/k 2 = C6H5, R1 = CH3)> = 10-2.The strain enthalpies Hs of 1 and 7 were calculated by the force field method.The results show that both steric effects are a result of the change in strain during the reaction s = 2Hs(7) - Hs(1)>.A fraction of 0.5 - 0.6 of Ds contributes to ΔG excit. (150 deg C), thus effecting the rate of the reaction.The large positiv value of Ds for R2 = aryl e.g.Ds (1a) = 7.8 kcal/mol, results from a strong repulsion between R1 and R2 in 7 due to the coplanar arrangement of the aryl ring with the radical center. - The resonance effect on the rate of thermolysis has a similar magnitude for R2 = phenyl, p-X-C6H4 (X = Cl, OCH3, t-C4H9, C6H5) and 2-naphthyl, but is considerable stronger for R2 = 1-naphthyl.The measured effect corresponds to a resonance stabilisation of 1-naphthylmethyl radicals by additional 4.5 kcal/mol, compared to benzyl radicals.

Thermolabile Hydrocarbons, XVIII. 1-Substituted Neopentyl radicals and their Dimers

Five 3,4-diaryl-2,2,5,5-tetramethylhexanes 1a - e were prepared as pure meso- and DL-isomers.According to the NMR spectra, x-ray analyses for meso- and DL-1e (with an (FB)2E conformation as energy minimum for DL-1e), and force field calculations the diastereomers have distinctly different minimum energy conformations, rotational potentials, and strain enthalpies.Also the activation parameters for the thermal dissociation into 1-arylneopentyl radicals 2 are typically differing.From an entropy discussion it is concluded that sandwich-like diastereomeric radical complexes are formed in these reactions as first intermediates.Their tightness influences ΔS%.The recombinations of the radicals 2 likewise take place stereoselectively.Their substituent effects on the selectivity can also be understood by primary formation of diastereomeric complexes of radical pairs.