70039-22-4

Upstream product

• 1254831-96-3 1-((3,5-di-tert-butyl-4-hydroxyphenyl)(p-tolyl)methyl)pyridin-2(1H)-one 
• 2444-28-2 2,6-di-tert-butyl-4-hydroxyphenol 
• 104-87-0 4-methyl-benzaldehyde 
• 106-44-5 p-cresol 
• 128-39-2 2,6-di-tert-butylphenol 

Downstream Products

• 1093168-99-0 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-(4-nitrophenyl)-3-p-tolylpropionitrile 
• 1097202-75-9 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-(diphenylphosphoryl)-3-(4-methylphenyl)propiononitrile 
• 1097202-67-9 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-2-(diethoxyphosphoryl)-3-(4-methylphenyl)propiononitrile 
• 1262969-11-8 C₂₈H₃₈O₂ 
• 1361954-46-2 4-((1H-imidazol-1-yl)(p-tolyl)methyl)-2,6-di-tert-butylphenol 

Relevant academic research and scientific papers

Solvent-free microwave synthesis 4 - phenyl methylene - 2, 6 - di-tert-butyl - 2, 5 - cyclohexadiene -1 - ketone (by machine translation)

The invention discloses a 4 - benzylidene - 2, 6 - di-tert-butyl - 2, 5 - cyclohexadiene - 1 - ketone derivative (P -QM) green preparation method. Under the condition of using solvent-free microwave radiation heating, 2, 6 - di-tert-butyl phenol and aldehyde, through the Mannich condensation and [...] two-step reaction, to obtain the 4 - benzylidene - 2, 6 - di-tert-butyl - 2, 5 - cyclohexadiene - 1 - ketone derivative (P -QM). This method has the raw material is cheap, the atom economy is high, fast reaction time, environment friendly, without the use of hazardous reagent and solvent, synthetic step is simple and convenient and the like, and the mild reaction conditions, substrate range wide applicability, simple and safe operation, and is suitable for industrial production. (by machine translation)

Unravelling the Nucleophilicity of Butenolides for 1,6-Conjugate Addition to p-Quinone Methides: A Direct Access to Diversely Substituted Butenolide-Derived Diarylmethanes

A Lewis acid catalyzed regioselective C-C bond is constructed through β-addition of deconjugated butenolides with p-quinone methides in a 1,6-conjugate addition manner. Interestingly, Lewis acid catalyzed vinylogous Mukaiyama-Michael reaction of silyloxyfurans with p-QMs proceeds selectively through the α or γ position exclusively. The reaction is mild with broad substrate scope, thus allowing easy access to a wide range of bis-arylated α-/β-/γ-substituted butenolides.

Copper-Catalyzed 1,6-Hydrodifluoroacetylation of para-Quinone Methides at Ambient Temperature with Bis(pinacolato)diboron as Reductant

An original and efficient copper-catalyzed 1,6-hydrodifluoroacetylation of para-quinone methides with difluoroalkyl bromides has been described with bis(pinacolato)diboron (B2pin2) as reductant. In this reaction, a new C(sp3)–CF2bond is constructed under smart conditions. A broad substrate scope of para-quinone methides (p-QMs) make this protocol very practical and attractive. Preliminary mechanistic studies manifested that a difluoroalkyl radical pathway was involved in this reaction. Also the presence of the diboron reagent was an essential requisite in this transformation. (Figure presented.).

Silver-Catalyzed Cascade 1,6-Addition/Cyclization of para-Quinone Methides with Propargyl Malonates: An Approach to Spiro[4.5]deca-6,9-dien-8-ones

An unprecedented silver-catalyzed cascade 1,6-addition/5-exo-dig cyclization reaction between para-quinone methides and propargyl malonates under mild reaction conditions has been described. This reaction provides an efficient method to construct versatile spiro[4.5]cyclohexadienones in moderate to excellent yields with high atom economy and scalability.

Ambident reactivities of pyridone anions

The kinetics of the reactions of the ambident 2- and 4-pyridone anions with benzhydrylium ions (diarylcarbenium ions) and structurally related Michael acceptors have been studied in DMSO, CH3CN, and water. No significant changes of the rate constants were found when the counterion was varied (Li+, K+, NBu4+) or the solvent was changed from DMSO to CH3CN, whereas a large decrease of nucleophilicity was observed in aqueous solution. The second-order rate constants (log k2) correlated linearly with the electrophilicity parameters E of the electrophiles according to the correlation log k2 = s(N + E) (Angew. Chem., Int. Ed. Engl. 1994, 33, 938-957), allowing us to determine the nucleophilicity parameters N and s for the pyridone anions. The reactions of the 2- and 4-pyridone anions with stabilized amino-substituted benzhydrylium ions and Michael acceptors are reversible and yield the thermodynamically more stable N-substituted pyridones exclusively. In contrast, highly reactive benzhydrylium ions (4,4′-dimethylbenzhydrylium ion), which react with diffusion control, give mixtures arising from N- and O-attack with the 2-pyridone anion and only O-substituted products with the 4-pyridone anion. For some reactions, rate and equilibrium constants were determined in DMSO, which showed that the 2-pyridone anion is a 2-4 times stronger nucleophile, but a 100 times stronger Lewis base than the 4-pyridone anion. Quantum chemical calculations at MP2/6-311+G(2d,p) level of theory showed that N-attack is thermodynamically favored over O-attack, but the attack at oxygen is intrinsically favored. Marcus theory was employed to develop a consistent scheme which rationalizes the manifold of regioselectivities previously reported for the reactions of these anions with electrophiles. In particular, Kornblum's rationalization of the silver ion effect, one of the main pillars of the hard and soft acid/base concept of ambident reactivity, has been revised. Ag + does not reverse the regioselectivity of the attack at the 2-pyridone anion by increasing the positive charge of the electrophile but by blocking the nitrogen atom of the 2-pyridone anion.

Electrophilicity parameters for benzylidenemalononitriles

Kinetics of the reactions of stabilized carbanions (derived from nitroethane, diethyl malonate, ethyl cyanoacetate, ethyl acetoacetate, acetyl acetone) with benzylidenemalononitriles have been determined in dimethyl sulfoxide solution at 20 °C. The second-order rate constants are employed to determine the electrophilicity parameters E of the benzylidenemalononitriles according to the correlation equation log k (20 °C) = s(E + N). Comparison with literature data shows that this equation allows the semiquantitative prediction of the reactivities of benzylidenemalononitriles toward a wide variety of nucleophiles, including carbanions, enamines, amines, water, and hydroxide.