Tetrakis(dimethylamino)ethylene Research Articles

Synthesis of 1,4-diketones: reaction of α-bromo ketones with tetrakis(dimethylamino)ethylene (TDAE)

1,4-Diketones were prepared by the reaction of α-bromo ketones with tetrakis(dimethylamino)ethylene (TDAE) in moderate to good yields. Similarly, α-bromo esters were reductively coupled using TDAE to give the 1,4-diesters in moderate yields.

Dedoping of organic semiconductors

An effective dedoping method for organic semiconductors using tetrakisdimethylaminoethylene (TDAE) was demonstrated using poly(3-hexylthiophene) thin film transistors in top gate configuration. Devices were treated after production and showed improved on/off ratios of up to 10 5 with little change in the field effect mobility.

Blaise Reaction of Ethyl 3-Bromodifluoromethyl-3-benzyloxyacrylate with Nitriles: A Convenient Synthesis of α-Difluorovinyl-Substituted β-Enaminoesters and β-Ketoesters

The Blaise reaction between the zinc dienolate of ethyl 3-bromodifluoromethyl-3-benzyloxyacrylate and a variety of nitriles gave a series of α-difluorovinyl substituted β-enaminoesters in good yield, which readily underwent hydrolysis to the corresponding β-ketoesters. Direct coupling of this zinc dienolate with acyl chloride also furnished the same α-difluorovinyl substituted β-ketoester, though in low yield, while the tetrakis(dimethylamino)ethylene (TDAE) mediated reaction provided γ-CF2 carbon and oxygen acylated products.

Nucleophilic Perfluoroalkylation of Aldehydes, Ketones, Imines, Disulfides, and Diselenides

Using a procedure analogous to that developed for nucleophilic trifluoromethylation, the perfluoroalkyl anion reagents created by mixing C2F5I and n-C4F9I with tetrakis(dimethylamino)ethylene (TDAE) were effective in their nucleophilic reactions with aldehydes, ketones, imines, disulfides, and diselenides. Irradiation proved beneficial in the aldehyde and ketone reactions.

Synthetic applications of ethyl 3-bromodifluoromethyl-3-benzyloxy-acrylate as a gem-difluorination building-block: Its reactions with aldehyde and epoxide

Synthetic applications of ethyl 3-bromodifluoromethyl-3-benzyloxy-acrylate as a versatile and multifunctionalized gem-difluorination building block to introduce difluoromethene subunit into some new hydroxy esters have been investigated. It was found that its zinc mediated reaction with a variety of aldehyde in DMF gave the Reformatsky reaction mode product, β-hydroxy ester, in good yield, while its tetrakis(dimethylamino)ethylene (TDAE) promoted reaction with a limited scope of aldehyde produced Barbier reaction mode product, δ-hydroxy ester, in moderate yield. The reaction of its zinc reagent with styrene oxide resulted in rearrangement of the epoxide to 2-phenyl-acetaldehyde, and then the zinc reagent condensed with this aldehyde to provide the Reformastsy reaction type product, β-hydroxy ester, in low yield.

Nucleophilic Difluoromethylation and Difluoromethylenation Using Bromodifluoromethyl Phenyl Sulfone.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Nucleophilic Addition of Ethyl 3-Bromodifluoromethyl-3-benzyloxyacrylate to Imines: An Effective Entry to Novel gem-Difluorinated Amino Esters and their Derivatives

Zinc- or tetrakis(dimethylamino)ethylene (TDAE)-mediated nucleophilic addition of ethyl 3-bromodifluoromethyl-3-benzyloxyacrylate to imines afforded gem-difluorovinyl substituted β-amino esters (α-addition product) and gem-difluorinated δ-amino esters (γ-addition product) or their cyclized derivatives, depending on the mediator and the nature of substituents on the imines.

Nucleophilic Trifluoromethylation of Imines Using the CF3I/TDAE Reagent.

The nucleophilic trifluoromethylation reagent derived from CF3I and tetrakis(dimethylamino)ethylene (TDAE) was found to be effective in addition to both N-tosyl aldimines and N-tolyl sulfinimines, the latter reaction exhibiting very good diastereoselectivity.

Nucleophilic difluoromethylation and difluoromethylenation using bromodifluoromethyl phenyl sulfone

Tetrakis(dimethylamino)ethylene (TDAE) was found to be an effective electron-transfer agent that promoted the reactions of bromodifluoromethyl phenyl sulfone with aldehydes to give structurally diverse (benzenesulfonyl)difluoromethylated alcohols in good yield, which can be further transformed into difluoromethyl alcohols and 1,1-difluoro-1-alkenes via reductive desulfonylation and Julia olefination, respectively.

Functionalization of 6-Nitrobenzo[1,3]dioxole with Carbonyl Compounds via TDAE methodology

We report herein the synthesis of substituted 2-(6-nitrobenzo[1,3]dioxol-5-yl)-1-aryl ethanols and 2-(6-nitrobenzo[1,3]dioxol-5-yl)-propionic acid ethyl esters from the reaction of 5-chloromethyl-6-nitrobenzo[1,3]dioxole with various aromatic carbonyl and α-carbonyl ester derivatives using the tetrakis(dimethylamino)ethylene (TDAE) methodology.

Nucleophilic Trifluoromethylation of Imines Using the CF3I/TDAE Reagent

The nucleophilic trifluoromethylation reagent derived from CF3I and tetrakis(dimethylamino)ethylene (TDAE) was found to be effective in addition to both N-tosyl aldimines and N-tolyl sulfinimines, the latter reaction exhibiting very good diastereoselectivity.

Reductive Debromination of 1,2‐Bis(bromomethyl)arenes Using Tetrakis(dimethylamino)ethylene (TDAE).

AbstractFor Abstract see ChemInform Abstract in Full Text.

Reductive debromination of 1,2-bis(bromomethyl)arenes using tetrakis(dimethylamino)ethylene (TDAE)

A new method for the reductive debromination of 1,2-bis(bromomethyl)arenes has been developed. The treatment of 1,2-bis(bromomethyl)benzene with tetrakis(dimethylamino)ethylene (TDAE) ( 1 ) in the presence of olefins gave 1,2,3,4-tetrahydronaphthalenes in moderate to good yields.

Nitrobenzylation of α‐Carbonyl Ester Derivatives Using TDAE Approach.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Reactions of Fluoroalkanesulfonyl Azides with Vinyl Ether and Tetrakis(dimethylamino)ethylene.

Abstract The reactions of fluoroalkanesulfonyl azides 1 with some electron-rich olefins have been studied. Alkyl vinyl ethers reacted with 1 readily at 0 °C or room temperature (RT) and did not give the corresponding N-fluoroalkanesulfonyl azilidines but 1-fluoroalkanesulfonyl-1,2,3-triazolines 3, which decomposed slowly at room temperature to form 1,4-fluoroalkanesulfonyl-2,5-alkoxyl-piperazines 4 with elimination of nitrogen gas. In contrast, more electron-rich alkene, tetrakis(dimethylamino)ethylene (TDAE) reacted with 1 affording N-fluoroalkanesulfonyl bis(dimethylamino)amidines 6 accompanying the release of N2. Reaction mechanisms are discussed.

Nitrobenzylation of α-carbonyl ester derivatives using TDAE approach

A series of 2-hydroxy-propionic acid ethyl ester derivatives was prepared in good yields by reaction of o- and p-nitrobenzyl chlorides ( 1 , 8 ) with various α-carbonyl esters in presence of tetrakis(dimethylamino)ethylene (TDAE). This reaction was generalized to α-ketolactam and α-ketomalonate.

Femtosecond photodissociation dynamics of van der Waals cationic clusters: a tool for detecting metastable isomers of organic cations

A femtosecond pump (266 nm)–probe (800 nm) experiment as been performed on small clusters of tetrakis(dimethylamino)ethylene (TDMAE) with argon (TDMAE(Ar) ≪10). The pump excites TDMAE and initiates deformations of the molecule within the cluster. Then, the probe ionises TDMAE and disposes enough excess energy in the cluster to evaporate all argon atoms. However, ionisation during the first 150 fs after the pump gives preferentially access to a metastable configuration of the TDMAE + ion, unquenched by the argon environment. This takes up enough of the excess energy to prevent complete argon evaporation. Observing the non-total-evaporation of weakly bond clusters formed of an organic cation with argon appears as a useful tool to reveal the existence of such metastable configurations in organic cations.

Nitrobenzylation of $alpha;-carbonyl ester derivatives using TDAE approach

A series of 2-hydroxy-propionic acid ethyl ester derivatives was prepared in good yields by reaction of o- and p-nitrobenzyl chlorides (1, 8) with various α-carbonyl esters in presence of tetrakis(dimethylamino)ethylene (TDAE). This reaction was generalized to α-ketolactam and α-ketomalonate.

Characterization of Laser Produced Tetrakis (Dimethylamino) Ethylene Plasma in a High-Pressure Background Gas

We present an interferometric and spectroscopic characterization of ultraviolet (UV) laser photoionization of a low ionization potential organic vapor, tetrakis (dimethylamino) ethylene (TMAE), seeded in high-pressure air component gases. These experiments are performed to explore the feasibility of using an electrodeless UV laser preionization of TMAE to initiate a plasma seeded in atmospheric pressure gases that can later be sustained by radiofrequency (RF) power by inductive wave coupling, thereby reducing the initiation RF power budget. A large volume (500 cc), high-density (/spl sim/10/sup 13/cm/sup -3/), electrodeless plasma is created by single-photon, 193 nm excimer laser ionization. 105 GHz millimeter-wave interferometry along with optical spectroscopy is employed to investigate the plasma formation and decay characteristics. The TMAE plasma decay mechanisms including two-body and three-body recombination with and without high pressure gases are examined and the dominant loss processes discussed and evaluated. Both density and optical emission measurements show a delay of 140 /spl plusmn/ 10 ns in the peak plasma density and emission indicating that the dominant ionization process is delayed ionization via excitation of super-excited states. The experiment also shows that TMAE remains a viable seed gas for UV ionization in the presence of air for t/spl les/10 min.

Reactions of fluoroalkanesulfonyl azides with vinyl ether and tetrakis(dimethylamino)ethylene

The reactions of fluoroalkanesulfonyl azides 1 with some electron-rich olefins have been studied. Alkyl vinyl ethers reacted with 1 readily at 0 °C or room temperature (RT) and did not give the corresponding N-fluoroalkanesulfonyl azilidines but 1-fluoroalkanesulfonyl-1,2,3-triazolines 3, which decomposed slowly at room temperature to form 1,4-fluoroalkanesulfonyl-2,5-alkoxyl-piperazines 4 with elimination of nitrogen gas. In contrast, more electron-rich alkene, tetrakis(dimethylamino)ethylene (TDAE) reacted with 1 affording N-fluoroalkanesulfonyl bis(dimethylamino)amidines 6 accompanying the release of N 2. Reaction mechanisms are discussed.