99334-84-6

Upstream product

• 623-26-7 terephthalonitrile 
• 67-56-1 methanol 
• 32445-98-0 2,3-bis(4-methoxyphenyl)-2,3-dimethylbutane 
• 127092-00-6 4-methoxybicumene 
• 127092-01-7 4-methoxy-4'-methylbicumene 
• 129970-59-8 4-methoxy-4'-cyanobicumene 
• 99334-82-4 2-(4-methoxyphenyl)-1,1-diphenyl-2-methylpropane 
• 7428-99-1 2-(4-methoxyphenyl)propan-2-ol 
• 118-75-2 chloranil 
• 22666-71-3 4-methoxycumyl cation 
• 1455-13-6 deuteromethanol 
• 74-88-4 methyl iodide 
• 4132-48-3 1-methoxy-4-(1-methylethyl)benzene 

Downstream Products

• 146803-00-1 1-(1,1-dimethyl-3-buten-1-yl)-4-methoxy-benzene 

Relevant academic research and scientific papers

Site-Selective Alkoxylation of Benzylic C?H Bonds by Photoredox Catalysis

Methods that enable the direct C?H alkoxylation of complex organic molecules are significantly underdeveloped, particularly in comparison to analogous strategies for C?N and C?C bond formation. In particular, almost all methods for the incorporation of alcohols by C?H oxidation require the use of the alcohol component as a solvent or co-solvent. This condition limits the practical scope of these reactions to simple, inexpensive alcohols. Reported here is a photocatalytic protocol for the functionalization of benzylic C?H bonds with a wide range of oxygen nucleophiles. This strategy merges the photoredox activation of arenes with copper(II)-mediated oxidation of the resulting benzylic radicals, which enables the introduction of benzylic C?O bonds with high site selectivity, chemoselectivity, and functional-group tolerance using only two equivalents of the alcohol coupling partner. This method enables the late-stage introduction of complex alkoxy groups into bioactive molecules, providing a practical new tool with potential applications in synthesis and medicinal chemistry.

Modulators of the Cystic Fibrosis Transmembrane Conductance Regulator Protein and Methods of Use

The invention discloses compounds of Formula (I), wherein A1, R1, R2, R3, R4, and n are as defined herein. The present invention relates to compounds and their use in the treatment of cystic fibrosis, methods for their production, pharmaceutical compositions comprising the same, and methods of treating cystic fibrosis by administering a compound of the invention.

Indium(i)-catalyzed alkyl-allyl coupling between ethers and an allylborane

An efficient method for alkyl-allyl cross-coupling between ethers and a 9-BBN-derived allylborane catalyzed by indium(i) triflate has been developed. The allylborane proved to be essential to obtain the desired products in high yields. The reaction displayed good substrate scope including high functional group tolerance. The Royal Society of Chemistry 2011.

Stabilized and Destabilized Carbocations in the 1,6-Methano[10]annulene Series

2-Chloromethyl and 3-chloromethyl-1,6-methano[10]annulene systems solvolyze in methanol to give simple substitution products. Solvent effect studies and the special salt effect support the involvement of cationic intermediates stabilized by the 1,6-methano[10]annulene group. Rate data indicate that the degree of cation stabilization greatly exceeds that of naphthyl groups. B3LYP/6-31G* computational studies also suggest that the cationic intermediates are greatly stabilized by the 1,6-methano [10] annulene. By way of contrast to these findings, solvolytic and computational studies indicate that the 11-(1,6-methano[10]annulenyl) cation is a destabilized analogue of the cycloheptatrienyl cation. There are no favorable interactions with the annulene ring. Distortions from planarity prevent charge delocalization as in the analogous aromatic cycloheptatrienyl cation.

Absolute reactivity of the 4-methoxycumyl cation in non-acid zeolites

The reactivity of the 4-methoxycumyl cation in a series of alkali metal cation-exchanged zeolites (LiY, NaY, KY, RbY CsY, NaX, NaMor, and Naβ) in the absence and presence of coadsorbed alcohols and water is examined using nanosecond laser flash photolysis. In dry zeolites, the absolute reactivity of the carbocation is found to be strongly dependent on the nature of the alkali counterion, the Si/Al ratio, and the framework morphology, with the lifetime of the carbocation in Naβ being almost 10000-fold longer than in CsY. The results suggest a mechanism for carbocation decay involving direct participation of the zeolite framework as a nucleophile, leading to the generation of a framework-bound alkoxy species. Intrazeolite addition reactions of alcohols and water to the 4-methoxycumyl cation can be described in terms of both dynamic and static quenching involving molecular diffusion through the heterogeneous topology and rapid coupling between the alcohol and the carbocation encapsulated within the same cavity. The dynamics of the quenching reactions are different from similar reactions in homogeneous solution due to both the passive and active influences of the zeolite environment. In a passive sense, the zeolite decreases the reactivity of the nucleophilic quencher by hindering molecular diffusion. However, the zeolite actively promotes the efficiency of intracavity coupling by enhancing the deprotonation of the oxonium ion intermediate, allowing the reaction to go to completion.

Star polymers having multiple polyisobutylene arms emanating from a calixarene core, initiators therefor, and method for the synthesis thereof

The synthesis and characterization of novel linear polymers and multi-arm star polymers comprising polyisobutylene arms connected to a well-defined calixarene core are described. The polymers are directly telechelic. They synthesis has been achieved using

Mesolytic scission of C-C bonds as a probe for photoinduced electron transfer reactions of Quinones

Photoinduced electron transfer reactions of chlorinated benzoquinones are investigated using bibenzylic donors that undergo rapid fragmentation upon oxidation. The fragmentation rates and the quantum yields are used to probe the dynamics of back-electron transfer (BET) in two types of radical ion pairs. The triplet ion pairs formed by interception of excited state quinones give products with high quantum yields. The singlet ion pairs formed by irradiation of the charge-transfer (CT) complexes between the quinones and the donors undergo reactions with significantly lower efficiency. The advantage of the first method (triplet quenching) over the CT-irradiation depends on the energetics of BET. It is large for reactions with relatively small ΔGet for BET and it decreases for reactions with more negative ΔGbet. The indirectly obtained rates of BET are in excellent agreement with literature data for similar, but unreactive systems, and the rates of C-C bond scission in radical cations generated in these systems are consistent with the thermodynamics of these processes.

A comparison of substituent effects on the stability of α,α-dimethylbenzyl carbocations in aqueous solution and in the gas phase: How significant is nucleophilic solvation?

Rate and equilibrium constants for conversion of ring-substituted cumyl alcohols in acidic solutions of 50:50 (v/v) trifluoroethanol/water (I = 0.50, NaClO4) to an equilibrium mixture of the corresponding cumyl alcohol, cumyl trifluoroethyl ether, and α-methylstyrene and the fractional yields of cumyl trifluoroethyl ether obtained from partitioning of the cumyl carbocation intermediates of these reactions between capture by water and by trifluoroethanol have been determined. These data and estimates of absolute rate constants for the reaction of ring-substituted cumyl carbocations with water in 50:50 (v/v) trifluoroethanol/water30 have been used to calculate equilibrium constants KR and Kp respectively for conversion of ring-substituted cumyl carbocations to the corresponding cumyl alcohols and α-methylstyrenes and the changes in Gibbs free energy (△Gx)sol for deprotonation of ring-substituted cumyl carbocations by α-methylstyrene. A plot of (△Gx)sol against (△Gx)gas for the corresponding reactions in the gas phase is linear with a slope of 0.70, in contrast to the previously reported unitary slopes of correlations of substituent effects on carbocation stability in solution and in the gas phase. We conclude that there is a modest increase in the stabilization of ring-substituted cumyl carbocations by solvation as their stability is decreased, but that this is much smaller than the change in stabilization by solvation with the changing stability of pyridinium and anilinium ions. The possible relevance of these data to the stabilization of carbocations by nucleophilic solvation is discussed.

Dicyanobenzene sensitized carbon-carbon bond cleavage in methoxybicumenes. Products and mechanistic studies

Radical cations of p-methoxy-p-X-bicumenes generated by ET to excited-state dicyanobenzene undergo rapid irreversible C-C bond scission giving cumyl cations and radicals. The photoefficiency of the process (Φ = 0.13 for X = MeO, Φ 0.005 for X = CN) and the fate of the radicals produced depends strongly on substitution.

Photochemically Generated Ion and Radical Pairs. Self-Destructive Charge-Transfer Complexes

Irradiation of CT complexes between 4-methoxy-4'-X-bicumenes, 1a-e (X = H, a; OMe, b; Me, c; CF3, d; CN,) and tetranitromethane (2) results in efficient generation of radical and ion pairs (Φ ca. 0.20).The identity of the final products depends on the dynamics of these pairs, which in turn is dramatically influenced by substitution and solvent.In all cases, 2*- dissociates rapidly ( - (4-) and NO2*.In CH2Cl2, 1a*- reacts with 4- (aromatic trinitromethylation) and undergoes C-C bond fragmentation before diffusional separation of fragments can occur.Thus, a tetrad of reactive intermediates (cumyl radical, NO2*, p-methoxycumyl cation and 4-) are produced in a single solvent cage.The cumyl radical is oxidized by 2, and both cumyl cations undergo α-trinitromethylation.The cumyl cations undergo trinitromethylation in the original solvent cage which is kinetically equivalent to a contact ion pair (CIP).In CH3CN the fragmentation is accompanied by aromatic nitration (radical collapse).In this solvent, the p-methoxycumyl cations produced by cleavage reaction undergo trinitromethylation at the CIP stage, but cumyl cations produced by thermal oxidation of the cumyl radicals are trapped by 4- at the solvent-separated ion pair stage.In CH2Cl2, 1b-c*+ undergo exclusively fragmentation, completely within the solvent cage.The cleavage of 1d-e*+ is much slower, and the radical cations undergo instead aromatic trinitromethylation.The observed substituent effect on the rate of cleavage ( ρ+ = -2.2) indicates significant charge transfer across the scissile bond in the transition state for this process.The products of these reactions are predominantly derived from ion annihilation.The radical coupling processes are limited to radical cation/radical collapse that lead to nitrated products.