13330-86-4

Upstream product

• 106-37-6 1.4-dibromobenzene 
• 4111-54-0 lithium diisopropyl amide 
• 92197-18-7 N, N-diisopropyl-O-benzoyl hydroxylamine 
• 183677-71-6 2-(4-bromophenyl)-5,5-dimethyl-1,3,2-dioxaborinane 
• 4107-98-6 N,N-diisopropylaniline 
• 108-86-1 bromobenzene 
• 108-18-9 diisopropylamine 

Downstream Products

• 1329423-30-4 4,4’-(buta-1,3-diyne-1,4-diyl)bis(N,N-diisopropylaniline) 
• 1431539-65-9 2-[4-(diisopropylamino)phenyl]-3-{[4-(diisopropylamino)phenyl]ethynyl}buta-1,3-diene-1,1,4,4-tetracarbonitrile 

Relevant academic research and scientific papers

Regiospecific metalation of oligobromobenzenes

The metalation of selected oligobromobenzenes with lithium diisopropylamide (LDA) was investigated. 1,3-Dibromo-substituted benzenes were metalated without special precautions since the resultant 2,6-dibromophenyllithium intermediates are relatively stabl

Systematic Evaluation of 1,2-Migratory Aptitude in Alkylidene Carbenes

Alkylidene carbenes undergo rapid inter- and intramolecular reactions and rearrangements, including 1,2-migrations of β-substituents to generate alkynes. Their propensity for substituent migration exerts profound influence over the broader utility of alkylidene carbene intermediates, yet prior efforts to categorize 1,2-migratory aptitude in these elusive species have been hampered by disparate modes of carbene generation, ultrashort carbene lifetimes, mechanistic ambiguities, and the need to individually prepare a series of 13C-labeled precursors. Herein we report on the rearrangement of 13C-alkylidene carbenes generated in situ by the homologation of carbonyl compounds with [13C]-Li-TMS-diazomethane, an approach that obviates the need for isotopically labeled substrates and has expedited a systematic investigation (13C{1H} NMR, DLPNO-CCSD(T)) of migratory aptitudes in an unprecedented range of more than 30 alkylidene carbenes. Hammett analyses of the reactions of 26 differentially substituted benzophenones reveal several counterintuitive features of 1,2-migration in alkylidene carbenes that may prove of utility in the study and synthetic application of unsaturated carbenes more generally.

Visible light-induced mono-bromination of arenes with BrCCl3

A highly efficient and regioselective bromination of electron-rich arenes and heteroarenes using commercially available BrCCl3as a “Br” source has been developed. The reaction was performed in air under mild conditions with photocatalyst Ru(bpy)3Cl2·6H2O, avoiding the usage of strong acids and strong oxidants. Mono-brominated products were obtained with medium to excellent yields (up to 94%). This strategy has shown good compatibility and highpara-selectivity, which will facilitate the complicated synthesis.

N-Arylphenothiazines as strong donors for photoredox catalysis – pushing the frontiers of nucleophilic addition of alcohols to alkenes

A new range of N-phenylphenothiazine derivatives was synthesized as potential photoredox catalysts to broaden the substrate scope for the nucleophilic addition of methanol to styrenes through photoredox catalysis. These N-phenylphenothiazines differ by their electron-donating and electron-withdrawing substituents at the phenyl group, covering both, σ and π-type groups, in order to modulate their absorbance and electrochemical characteristics. Among the synthesized compounds, alkylaminylated N-phenylpheno-thiazines were identified to be highly suitable for photoredox catalysis. The dialkylamino substituents of these N-phenylpheno-thiazines shift the estimated excited state reduction potential up to ?3.0 V (vs SCE). These highly reducing properties allow the addition of methanol to α-methylstyrene as less-activated substrate for this type of reaction. Without the help of an additive, the reaction conditions were optimized to achieve a quantitative yield for the Markovnivkov-type addition product after 20 h of irradiation.

N -Alkyl substituted 1 H -benzimidazoles as improved n-type dopants for a naphthalene-diimide based copolymer

Doped polymer semiconductors are actively studied for opto- and micro-electronic applications including thermoelectric generators, where a high electrical conductivity is a key factor. In general, n-type doping is more challenging to achieve than p-type doping. Here we study n-type doping of a commonly used electron transporting naphthalene-diimide bithiophene copolymer with a series of air-stable and solution-processable benzimidazole dopants. To understand the role of dopant structure on miscibility and the resulting conductivity, benzimidazoles with different linear and branched alkyl substituents were synthesized, and their doping efficacy compared through combined morphological, electrical and thermoelectric characterization. We observe a clear dependence of the nature of the alkyl substituent on dopant intercalation into the semicrystalline morphology. By increasing the length or the steric hindrance of the alkyl substituents, the miscibility between dopant and copolymer is enhanced leading to optimized electrical conductivity.

Energy Gap between the Poly-p-phenylene Bridge and Donor Groups Controls the Hole Delocalization in Donor-Bridge-Donor Wires

Poly-p-phenylene wires are critically important as charge-transfer materials in photovoltaics. A comparative analysis of a series of poly-p-phenylene (RPPn) wires, capped with isoalkyl (iAPPn), alkoxy (ROPPn), and dialkylamino (R2NPPn) groups, shows unexpected evolution of oxidation potentials, i.e., decrease (-260 mV) for iAPPn, while increase for ROPPn (+100 mV) and R2NPPn (+350 mV) with increasing number of p-phenylenes. Moreover, redox/optical properties and DFT calculations of R2NPPn/R2NPPn+? further show that the symmetric bell-shaped hole distribution distorts and shifts toward one end of the molecule with only 4 p-phenylenes in R2NPPn+?, while shifting of the hole occurs with 6 and 8 p-phenylenes in ROPPn+? and iAPPn+?, respectively. Availability of accurate experimental data on highly electron-rich dialkylamino-capped R2NPPn together with ROPPn and iAPPn allowed us to demonstrate, using our recently developed Marcus-based multistate model (MSM), that an increase of oxidation potentials in R2NPPn arises due to an interplay between the electronic coupling (Hab) and energy difference between the end-capped groups and bridging phenylenes (Δ?). A comparison of the three series of RPPn with varied Δ? further demonstrates that decrease/increase/no change in oxidation energies of RPPn can be predicted based on the energy gap Δ? and coupling Hab, i.e., decrease if Δ? ab (i.e., iAPPn), increase if Δ? > Hab (i.e., R2NPPn), and minimal change if Δ? ≈ Hab (i.e., ROPPn). MSM also reproduces the switching of the nature of electronic transition in higher homologues of R2NPPn+? (n ≥ 4). These findings will aid in the development of improved models for charge-transfer dynamics in donor-bridge-acceptor systems.

Copper-Catalyzed Electrophilic Amination of Organoaluminum Nucleophiles with O -Benzoyl Hydroxylamines

A copper-catalyzed electrophilic amination of aryl and heteroaryl aluminums with N,N-dialkyl-O-benzoyl hydroxylamines that affords the corresponding anilines in good yields has been developed. The catalytic reaction proceeds very smoothly under mild conditions and exhibits good substrate scope. Moreover, the developed catalytic system is also well suited for heteroaryl aluminum nucleophiles, providing facile access to heteroaryl amines.

Practical catalytic method for synthesis of sterically hindered anilines

A practical catalytic method for the synthesis of sterically hindered anilines is described. The amination of aryl and heteroaryl boronic esters is accomplished using a catalyst prepared in situ from commercially available and air-stable copper(i) triflat

Donor-acceptor (D-A)-substituted polyyne chromophores: Modulation of their optoelectronic properties by varying the length of the acetylene spacer

A series of donor-acceptor-substituted alkynes, 2 a-f, was synthesized in which the length of the π-conjugated polyyne spacer between the N,N-diisopropylanilino donor and the 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) acceptor was systematically changed. The

Synthesis of hindered anilines: Copper-catalyzed electrophilic amination of aryl boronic esters

No longer a hindrance: Copper-catalyzed electrophilic amination of aryl boronic esters is accomplished under mild reaction conditions using 2.5-5.0 mol % of a catalyst derived from copper tert-butoxide and Xantphos ligand (see scheme). The reaction tolerates a wide range of functional groups and can be used to prepare some of the most hindered anilines made to date. Copyright